Def RE7. Skyrim is the best VR game out there IMO (not sure how it it is on PSVR), so I'm glad you have that.
I have an oculus so RE7 isn't available on PC in VR, but here are some games I love that are also on PSVR.
Space Pirate Trainer. This game is fuckin incredible. Make it your first one, as it's easy to pick up and mind blowing for a first try. Great to show friends too. People who slam VR haven't played this, otherwise they'd have a new appreciation for it. You are basically the ship in Galaga. It feels like an 80's sci-fi movie come to life.
SuperHot. This is the closest thing to the Matrix you can experience, so damn cool nand challenging
Arizona Sunshine. I really enjoyed the hell out of this game, totally feels like you're in the walking dead.
Beat Saber. Another easy to pick up game, and great for friends. It's so damn fun and also a good challenge
For PSVR exclusives. Wipeout VR. This is the best racing game (PRoject Cars 2 a close second) in VR IMO, and I've tried most of them. It looks and plays incredible and has tons of options for comfort. I almost bought a PSVR for it.
I heard Farpoint is good too, but I haven't tried it.