I don't know if the the Steam PlayStation VR2 app is essential, but if it is you may be limited in launching ED via Steam.
It is possible via your Frontier account to apply for a Steam passkey to run your native ED version via Steam, I did this for one of my copies of the game.
You could also try adding the /vr binary to the Target line as below and see if the game launches in VR.
My game location is as follows.
Note the " marks around the path which is essential
"C:\Program Files (x86)\Frontier\EDLaunch\EDLaunch.exe" /vr
Other than that I don'r really have any more ideas as I use a Meta Quest 3 not a PS Headset.