First a disclaimer: I do not expect this answer to be exhaustive. BG3 is a large game, with a lot of content. In part because of that, I will be focusing on the broad categories, rather than individual miscellanea.
Character Options
D&D 5e has been out for multiple years, and has over a dozen sourcebooks. While Baldur's Gate 3 (BG3) has a large variety, and covers most of the "traditional" fantasy options, there are gaps between what is available as a character option in the game versus the tabletop.
This encompasses such varied categories as race (there are Elves, but no Changelings), subrace (where e.g. Githyanki is available, but not Githzerai), sub-class (e.g. "Trickery" domain, but not "Twilight"), feats ("Durable", but not "Elven Accuracy"), spells ("Fireball", but not "Greenflame Blade"), clerical gods ("Mystra", but no "Cyric") and even class (sorry, Artificer...).
There's also the fact that the game caps out at level 12 - generally speaking, there are no 7th level spells at all, and other high-end class abilities are likewise not implemented.
Multi-classing, however, does not have ability score requirements at all.
The long and short of it is, if the character option is unavailable, it is much more likely that it is never available, rather than simply inaccessible.
Mechanical Differences
Some spells and abilities are simply different in BG3. "Spell Sniper", for instance, does not allow free range pick of any qualifying cantrip, but instead gives a 4-spell list to choose from; A Paladin's Lay on Hands isn't the flat 5 HP / level "pool", but rather a charged ability which derives its potency from class level instead; A cleric's "Spiritual Weapon" spell summons an actual entity that can be damaged (and destroyed), but no longer requires the cleric to spend their bonus action to command it to attack.
This is the category that is going to differ most wildly for someone with prior experience with 5e D&D.
A special nod towards shapeshifting (wildshape et al) -- many reactions are unavailable while shapeshifted, even if mechanically they would work fine (such as Tempest cleric's "Wrath of the Storm").
Weapon Abilities
Martial characters in BG3 have slightly more options when it comes to fights -- each weapon they are proficient with gains access to one or more "weapon abilities" that can be used in place of a regular attack (or in addition to). The closest analaogue would be Battlemaster manuevers, with each one being usable once / short rest.
Action Economy
The action economy is quite different. First, "Shove" is now a bonus action, instead of being tied to the "Attack" action (though it's still based on strength -- good luck, Wizards), as is "Jump" (instead of being handled as part of movement).
As your other question observes, there is no "loading" penalty on crossbows (and Crossbow Expert is tweaked to provide a different bonus instead), which leads to everyone being able to make bonus action attacks with an off-hand hand crossbow or light weapon (even when you haven't taken the "Attack" action).
There is no rule that limits casters to cantrips if they cast a spell using a bonus action.
And lastly, falling prone immediately ends your turn.
Resting
Long resting requires an in-game resource (Camp Supplies) to trigger, but can be triggered essentially any time outside of combat. Short rests are more limited -- only two are allowed between long rests, and they always restore exactly 50% of your HP, no hitdice required.
Certain item effects and spells last "until your next long rest", rather than a duration in days or hours. (such as Longstrider, or an Elixir of Hill Giant Strength)
Conclusion
Ultimately, I think most of the "Gotchas" come from the "Action Economy" heading -- other differences tend to be much more readily apparent from their descriptor, whereas these exceptions are never explicitly spelled out (after all, BG3 doesn't have a "PHB" of its own describing the rules!).
I think in general it is probably ideal to not worry overly much about whether or not BG3 is a perfect translation of D&D 5e into the virtual space (as this answer indicates, it isn't), but rather enjoy it on its own, for what it is.