Do note, there's a very high possibility that you may get motion sickness (like me!) when playing games where the camera moves and you stay still.
I'd highly recommend trying out the jungle level in VR playroom first before getting games like RE7 or Skyrim where's there's free movement.
As for games that totally justify the PSVR, my personal recommendations are:
VR Playroom - Goes without saying, this is the very first thing you should play.
Mortal Blitz - 5 levels of shooting action that can get REALLY intense depending on how high you set the difficulty. Decent production values.
DOOM VFR - I'm only at level 2 so far but I really like it. It has free movement as well as teleportation AND you can strafe and move forwards/backwards to dodge enemy shots.
You'll definitely need 2 PS Move controllers to enjoy the games.
If you're ok with anime-style stuff, I'd also recommend Summer Lesson (please don't buy this at full price) and the free Fate/Grand Order VR Experience (which is more a time waster than an actual game) on the Japanese PSN where you get to socialise with Mash Kyrielight and Artoria Pendragon.
BUT WAIT THERE'S MORE!
Do you have a powerful PC? Feel like playing stuff on your PC with your PSVR?
Trinus PSVR is the answer:
https://www.trinusvirtualreality.com/psvr/
Here's a Youtube tutorial on how to set it up:
https://www.youtube.com/watch?v=5BSeXv3KRaw
But what about the controllers? There's open source software out then that will make the PS Move controllers work on a PC, but I took the lazy way out:
There's a company in China that makes a substitute for Steam VR controllers:
https://www.nolovr.com/store/pre-order-regular-nolo-set.
The product page has a link to the Amazon US store where you can order them. Half the reviews say it's garbage, the other half say it's great.
I'm going to find out for myself in 2 weeks time when my set arrives...