The app seems to be Waiting for Review. Refreshing the page should get both statuses in sync again. If that doesn't work, you could also verify the status in a different browser or the App Store Connect iOS app.
ConfuseIous
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After a lot of experimentation, I have found a workaround.
Open the Apple Watch app on iOS
Scroll down until you see your app name, tap it and disable Show App on Apple Watch
Go back to Xcode and try to run the app on your Apple Watch again, the app should work now and allow you to use the debugger too.
Hey guys, I had this same issue but referred to https://developer.apple.com/forums/thread/53659 , after which the Watch app works as expected. I still get the entry point error but it doesn't seem to affect anything.