Yes, you can have multiple headsets on one account. However, there can potentially be certain problems. If an app has implemented cloud saves (like Phantom Covert Ops), even though each person has a headset, they will will both still be sharing the same game save. Meaning if you make progress, then when the other person gets on their headset, they will be where you left off.
Second, for the most part you won't be able to play multiplayer games between them unless the game has implemented its own account system. For example, Rec Room has you make a separate Rec Room account, so each of you would be able to play together by logging on to separate Rec Room accounts.
i7 8700, 16GB, RTX 2080 TI, Rift CV1 | i5 4690K, 16GB, GTX 1660 TI, Rift CV1 | Quest | Quest 2