Resident Evil: Complete the game with either Jill or Chris. There are some differences, but you'll still experience most of the game's content with either one. I recommend Jill because she gets more inventory slots, more different weapons, and Barry as a partner instead of Rebecca.
Optional content: Chris's story is pretty much it, though clearing the game in less than three hours lets you have an infinite rocket launcher if you load the NG+ clear file. Chris and Jill also both have multiple endings depending on what you do (or don't do).
RE2: After completing one character's story, you can play the other's "B" story by loading the clear file on the other disc. Claire A/Leon B is canon.
Optional content: Other than Leon A/Claire B, completing any route with an A rank (gained for finishing quickly, without using First Aid Sprays, and with only a few saves) unlocks The 4th Survivor, where you start in the sewers and have to escape the police station. You start with a lot of supplies, but can't pick up more. If you miss the A rank, don't worry too much about it.
RE3 Nemesis: There's only one story. Some minor things are randomized and a couple of branching paths appear, though they all lead to the exact same place anyway. There's an option for 'Easy' or 'Hard' mode instead; I recommend Hard mode, which is essentially Normal. Easy gives you almost all the weapons and lots of First Aid Sprays to start off, and Nemesis won't drop anything if you manage to mug him.
Optional content: Beating the game unlocks Mercenaries mode, though it's pretty different from how it appears in later games, being closer to 4th Survivor. You have a limited time to escape the city, with more time being earned for killing enemies and rescuing hostages. Clearing this mode is how you unlock infinite rocket launchers and the like. You also get graded after beating the main story, and it's a lot harsher than 2's grading.
RE1 Remake: As with the original game, completing either Chris's or Jill's story is enough. Again, I think Jill is generally more fun, though it may be worth trying the character you didn't pick for the original. Also, the difficulty selection is a bit abstract; since hard mode is locked at the start, the highest difficulty offered on the form 'Mountain Climbing' is the normal mode.
Optional content: 'Once Again' is the NG+ mode unlocked by clearing the game. Beating that unlocks 'Real Survival', where item boxes aren't linked. Beating that unlocks 'Invisible Enemy' mode, which is what it sounds like.
RE4: All that matters is difficulty; at base you have Easy or Normal. I recommend Normal, because Easy is not only way too easy, it outright removes content from the game. Clearing Normal unlocks Professional difficulty, which will really give you a run for your money.
Optional content: Separate Ways adds a minor amount of detail to the story, but honestly it kinda sucks; the only reason to do it is to unlock the Special 2 costume. Assignment Ada is even more pointless. The Mercenaries is back in the form of an arcade shooter, and while I could never get the hang of it it's a lot more fun than it was in RE3.
RE5: The choice between Chris and Sheva is largely moot; though they are occasionally required to split up, it's rare that their separate paths are forced to be a specific way. Again, difficulty options are the meat here, and again I recommend Normal over Veteran or Amateur.
Optional content: 'Lost in Nightmares' and 'Desperate Escape' are two DLC scenarios that basically act like Separate Ways for RE4; they come free with the Gold Edition so you can't not get them. Also, Mercenaries is back and it has co-op now. Honestly I think this is the most fun part of the game. Each mission also has several BSAA Emblem targets that you can shoot for 100% completion.
RE6: Four stories, eight characters (four teams of two). Each character has a slightly different loadout, but it's probably not worth worrying about, other than that Ada's partner is so bad he can't even interact with puzzles. It is necessary to play every route to see the full story, but a fair bit of stuff gets repeated. Also, the in-game tutorial legitimately sucks.
Optional content: More co-op Mercenaries is about it, other than the return of BSAA Emblems from 5. There's a lot more of them now, and each one gives you a lore file; the story makes no sense without them, and barely makes sense with them too.
RE7 Biohazard: Back to having one story mode again. Easy and Normal available at the start, 'Madhouse' once you clear it completely changes the item locations on top of having tougher enemies and limited saves.
Optional content: There's a whole slew of DLC chapters, but most of them don't add much. The important ones are 'Not a Hero' (free) and 'End of Zoe'.
RE2 Remake: Like the original, completing one character's story unlocks a B-side for the other, called '2nd Run'. The story changes are somewhat less impactful than the original, but the item layouts are massively changed like in Madhouse mode. Hardcore difficulty is available from the start, but I don't recommend it for a first run. Leon A/Claire B is canon this time, but not as strongly as before.
Optional content: 'The Ghost Survivors' is unlocked by clearing either character's 2nd Run, adding three 'what if' scenarios for three characters who died in the main game surviving and escaping Raccoon City. 'The 4th Survivor' also returns if you can clear the A-rank time for any route (grading is exclusively based on time now).
RE3 Remake: Like the original, there's only one story path, and unlike the original the extremely minor branching paths and random puzzle solutions are gone. Hardcore isn't as bad as in RE2, but...
Optional content: Finishing Hardcore unlocks 'Nightmare' difficulty, and beating that unlocks 'Inferno'. Other than that, there isn't much else to do here.
RE Village: The hard difficulty is available from the start, and beating the game unlocks the expert mode 'Village of Shadows'. VoS is completely ridiculous.
Optional content: Mercenaries makes a return, and if you're willing to shell out for DLC there's also 'Shadows of Rose' in the Winters Expansion DLC, which I won't explain because it's a pretty big spoiler.
RE4 Remake: Hardcore difficulty is available from the start; it's easier than the original Professional but much harder than OG Normal. Standard is pretty close to OG Normal at least, or you can try Hardcore if you're confident.
Optional content: Mercenaries is a free DLC, and Separate Ways is a paid DLC. Out of all the paid DLCs for all the games that have them, it's the only one I outright recommend buying; it's a huge improvement over the original Separate Ways, and isn't that expensive because it's not bundled with other crap. 'Not a Hero' and the RE5 DLCs are free, so they don't count.
I've never played Code Veronica, 0, or either Revelations game, so you're on your own for those sadly.
Optional content: Chris's story is pretty much it, though clearing the game in less than three hours lets you have an infinite rocket launcher if you load the NG+ clear file. Chris and Jill also both have multiple endings depending on what you do (or don't do).
RE2: After completing one character's story, you can play the other's "B" story by loading the clear file on the other disc. Claire A/Leon B is canon.
Optional content: Other than Leon A/Claire B, completing any route with an A rank (gained for finishing quickly, without using First Aid Sprays, and with only a few saves) unlocks The 4th Survivor, where you start in the sewers and have to escape the police station. You start with a lot of supplies, but can't pick up more. If you miss the A rank, don't worry too much about it.
RE3 Nemesis: There's only one story. Some minor things are randomized and a couple of branching paths appear, though they all lead to the exact same place anyway. There's an option for 'Easy' or 'Hard' mode instead; I recommend Hard mode, which is essentially Normal. Easy gives you almost all the weapons and lots of First Aid Sprays to start off, and Nemesis won't drop anything if you manage to mug him.
Optional content: Beating the game unlocks Mercenaries mode, though it's pretty different from how it appears in later games, being closer to 4th Survivor. You have a limited time to escape the city, with more time being earned for killing enemies and rescuing hostages. Clearing this mode is how you unlock infinite rocket launchers and the like. You also get graded after beating the main story, and it's a lot harsher than 2's grading.
RE1 Remake: As with the original game, completing either Chris's or Jill's story is enough. Again, I think Jill is generally more fun, though it may be worth trying the character you didn't pick for the original. Also, the difficulty selection is a bit abstract; since hard mode is locked at the start, the highest difficulty offered on the form 'Mountain Climbing' is the normal mode.
Optional content: 'Once Again' is the NG+ mode unlocked by clearing the game. Beating that unlocks 'Real Survival', where item boxes aren't linked. Beating that unlocks 'Invisible Enemy' mode, which is what it sounds like.
RE4: All that matters is difficulty; at base you have Easy or Normal. I recommend Normal, because Easy is not only way too easy, it outright removes content from the game. Clearing Normal unlocks Professional difficulty, which will really give you a run for your money.
Optional content: Separate Ways adds a minor amount of detail to the story, but honestly it kinda sucks; the only reason to do it is to unlock the Special 2 costume. Assignment Ada is even more pointless. The Mercenaries is back in the form of an arcade shooter, and while I could never get the hang of it it's a lot more fun than it was in RE3.
RE5: The choice between Chris and Sheva is largely moot; though they are occasionally required to split up, it's rare that their separate paths are forced to be a specific way. Again, difficulty options are the meat here, and again I recommend Normal over Veteran or Amateur.
Optional content: 'Lost in Nightmares' and 'Desperate Escape' are two DLC scenarios that basically act like Separate Ways for RE4; they come free with the Gold Edition so you can't not get them. Also, Mercenaries is back and it has co-op now. Honestly I think this is the most fun part of the game. Each mission also has several BSAA Emblem targets that you can shoot for 100% completion.
RE6: Four stories, eight characters (four teams of two). Each character has a slightly different loadout, but it's probably not worth worrying about, other than that Ada's partner is so bad he can't even interact with puzzles. It is necessary to play every route to see the full story, but a fair bit of stuff gets repeated. Also, the in-game tutorial legitimately sucks.
Optional content: More co-op Mercenaries is about it, other than the return of BSAA Emblems from 5. There's a lot more of them now, and each one gives you a lore file; the story makes no sense without them, and barely makes sense with them too.
RE7 Biohazard: Back to having one story mode again. Easy and Normal available at the start, 'Madhouse' once you clear it completely changes the item locations on top of having tougher enemies and limited saves.
Optional content: There's a whole slew of DLC chapters, but most of them don't add much. The important ones are 'Not a Hero' (free) and 'End of Zoe'.
RE2 Remake: Like the original, completing one character's story unlocks a B-side for the other, called '2nd Run'. The story changes are somewhat less impactful than the original, but the item layouts are massively changed like in Madhouse mode. Hardcore difficulty is available from the start, but I don't recommend it for a first run. Leon A/Claire B is canon this time, but not as strongly as before.
Optional content: 'The Ghost Survivors' is unlocked by clearing either character's 2nd Run, adding three 'what if' scenarios for three characters who died in the main game surviving and escaping Raccoon City. 'The 4th Survivor' also returns if you can clear the A-rank time for any route (grading is exclusively based on time now).
RE3 Remake: Like the original, there's only one story path, and unlike the original the extremely minor branching paths and random puzzle solutions are gone. Hardcore isn't as bad as in RE2, but...
Optional content: Finishing Hardcore unlocks 'Nightmare' difficulty, and beating that unlocks 'Inferno'. Other than that, there isn't much else to do here.
RE Village: The hard difficulty is available from the start, and beating the game unlocks the expert mode 'Village of Shadows'. VoS is completely ridiculous.
Optional content: Mercenaries makes a return, and if you're willing to shell out for DLC there's also 'Shadows of Rose' in the Winters Expansion DLC, which I won't explain because it's a pretty big spoiler.
RE4 Remake: Hardcore difficulty is available from the start; it's easier than the original Professional but much harder than OG Normal. Standard is pretty close to OG Normal at least, or you can try Hardcore if you're confident.
Optional content: Mercenaries is a free DLC, and Separate Ways is a paid DLC. Out of all the paid DLCs for all the games that have them, it's the only one I outright recommend buying; it's a huge improvement over the original Separate Ways, and isn't that expensive because it's not bundled with other crap. 'Not a Hero' and the RE5 DLCs are free, so they don't count.
I've never played Code Veronica, 0, or either Revelations game, so you're on your own for those sadly.
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