First dabble in the tutorials and easy to get used to apps like The Lab. You don't want to go too crazy for the first few experiences.
What kind of games do you like to play, that's kinda like asking just any PC game out of the thousands... Single player, co-op, PVP, FPS, action, adventure, puzzle, sports, what.
Vox Machinae is a great multiplayer mech combat game, mostly PVP but also with co-op content in recent updates. The cockpit feel is amazing.
Budget Cuts is a cool stealth action puzzle game with nicely integrated teleport mechanics, the bigger better sequel is coming soon.
Apex Construct is a good sci fi action adventure game with archery systems at its core.
The Thrill of the Fight is a great boxing game, less fancy than Creed and its Rocky license but a really good sim.
Pistol Whip is the new kid on the rhythm game block, I love it and don't even play it as a rhythm game but as some funky cool new Virtua Cop-like (normally it has aim assist so you just dodge bullets and fire on the beat, but you can make it so it requires proper aiming).
In Death is a great archery based rogue-lite I spent many hours in early on, it has cool teleportation methods as well as free locomotion now.
SUPERHOT VR is a great little puzzle action game showing cool interactivity/physics/slow motion mechanics.
Racket Fury is a polished little table tennis game.
Catch & Release is a nifty fishing game.
Red Matter is a very immersing and beautiful and also (to me) challenging pure adventure game with a great setting.
Moss is a fun little third person action adventure, you guide a sword wielding mouse around as if you're looking at a diorama of a fairy tale and occasionally also interact with your hands to clear a path or solve a puzzle.
Space Junkies is a PVP zero gravity arena FPS, like Quake or Unreal in space, good for some instant mindless action. Ubisoft is done with it but it's highly polished anyway.
Ultrawings is a nice flight game, not quite a sim, maybe a bit like pilot wings, goals and stuff to get through.
Windlands 2 is a cool action adventure with not-web swinging and archery. Also co-op capable.
Raw Data is probably the best of the arena/wave type shooter games with different classes, some progression and co-op.
Onward is my favorite "standard" FPS, PVP focused as all but it has co-op I find myself returning to despite dodgy hacky AI. It has the best weapons and gadgets handling in my opinion, if Pavlov is Counter-Strike and Contractors Call of Duty then this is Ghost Recon (the old good ones).
Lone Echo is a must play immersing adventure and so is the free Echo VR/Arena and its $10 Combat DLC which take those zero gravity mechanics to online PVP sports and class based combat modes.
Journey of the Gods is a really nice Zelda-lite (it's small scale, short, linear and segmented in levels - even if it's somewhat disguised - rather than an open seamless adventure but the core systems are fun and the story and setting neat).
VTOL VR is a great simulation style flight game, still light on content and not the most beautiful but with a wonderfully interactive cockpit and deep systems for two different types of (military) aircraft.
Blade & Sorcery has the best physics based melee combat but doesn't yet have progression and upgrades implemented in the current early access release.
There are many great early access games as the two above, I really like where Vengeful Rites is going as a VR RPG action adventure for example.
There's also the free-for-now A Township Tale to try for some online rpging/surviving/crafting shenanigans.
Oh and Espire 1 just released and looks like a fun time as a stealth focused FPS but we'll see if people discover any glaring issues beyond its decidedly low production values and cut corners. Edit: nope, not so good after all, dammit (imo).