I've tried out quite a few games on this now, some quick impressions below.
Call of the Mountain - Probably the best game visually, seeing the dinosaurs up close is very cool. I only have limited experience with PSVR and never had the Move controllers, so am enjoying messing around with the hand movements and picking up and throwing items etc. Probably less exciting for any veterans of VR.
Rez Infinite - I've never quite 'got' the hype over Rez and have only played it briefly a few times over the years and many re-releases. That said, the eye-tracking aiming is very cool and like Jiggles said it feels like you're essentially controlling things with your mind as the only button you're actually pressing is X.
No Man's Sky - Played this a fair bit at launch but haven't revisited since, it almost seems like a new game now with the all of the updates so looking forward to playing more. The VR implementation is very cool, with the menus etc. being linked to computers on your gloves. The first time taking off from a planet and flying into space was great.
Pavlov - I am rubbish at this but think it might be my favourite game. Manually reloading yourself just feels very good to do for some reason. I am struggling slightly with the aiming, I'm not sure the shape of the controllers suits aiming down the sights of a gun but I'm hoping to get used to that and looking forward to playing more.
Thumper - Just as fantastic as it always was.
Drums Rock - If you like Guitar Hero and Rock Band you'll like this. The haptics do a good job of giving feedback when you're hitting the sticks and drums, and throwing the sticks in the air while you play just feels fun.
Gran Turismo 7 - Pretty fantastic, driving games are not my favourite genre but I've been having a lot of fun with this over the last few weeks and VR just adds so much to the experience. I imagine this would be very immersive with a steering wheel and pedals etc. for the driving game enthusiasts.
Kayak VR Mirage - Very relaxing game with great visuals. Definitely a good showcase for newer players. My wife had a go last night and pushed a penguin over with a paddle, and she felt genuinely guilty about it for like an hour afterwards
True VR immersion!