I had the same issue when building from Unity (a new visionOS project from scratch in XCode worked just fine, I would recommend sanity-checking this first).
The solution that worked for me was to update the Player Settings in Unity like so:
“Player > Other Settings > Configuration > Target SDK > Simulation”
If you then Build your project and open in XCode, you should see the Vision Pro simulator populate in the "Run Destinations" dropdown menu.
Topic:
Developer Tools & Services
SubTopic:
Xcode
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