I've played it in VR for a few hours. Overall it's fun but there are some caveats.
The controls in VR are quite good. With the Moves locomotion is very similar to Skyrim and all crafting and upgrade options are available via a hologram interface on each of your gloves. Driving your planetside vehicles with the Moves works very well and is a lot of fun, especially the Nomad. Pilloting ships with the Moves is tricky as the controls are too sensitive. Luckily, you can switch between Moves and DS4 at wil by just pressing a button on either controller. As such you can for example use the Moves when on foot and switch to the DS4 when piloting your ship or other vehicles.
When the game first dropped there were severe framerate issues. I bypassed those by disabling multiplayer support and framerate has been rock steady since. Hello Games has also been rolling out lots of patches; I think they've aready put up 6 since the upgrade dropped and they continue to monitor and support the game, so the network issues may have improved but I really haven't bothered to look into them. The game also crashed a couple of times that first day but has been stable since.
The scale of the universe is great in VR; you ships look massive as you approach them and the fauna on alien planets can be small and cute or towering and downright dangerous (I had a close encounter with what was basically a raptor with horns that left me a little shaken). Looking up at giant planets from the surface of a world or from the cockpit of your ship is quite impressive and the space stations look suitably massive.
The biggest downside so far is that the visuals are quite soft and anything further than 10-12 feet away from you can be pretty blurry; it's somewhat similar in visual quality to Skyrim when it first dropped. For me the sense of immersion mitigates this and after a few minutes I just get sucked into the world and forget the blurriness; but it is there and can be an issue if that sort of thing bothers you.
The game does not appear to have Pro support at this point. Several streamers pointed out that it looked considerably sharper on the Pro during previews that they attended. Hopefully Pro support is still incoming and will improve the resolution somewhat if/when it gets here.
Overall, if you enjoy the gameplay loop then VR will probably pull you further into its world, soft visuals nothwithstanding. If you didn't get anything out of the flat game, it may still be worth a shot to check it out again as even without VR the game is very different from what it was at launch - story missions, quests, jobs & contracts, base building, exocraft to play with, etc. You can even start up a game in Creative Mode and bypass the grinding necessary to craft items, build bases and buy new ships.