To narrow things down, try these steps:
- Restart the computer (of course)
- Re-start in Safe Mode. This bypasses certain potentially disruptive processes, and it often helps. Safe Mode is different for different computers, so see this:
Start up your Mac in safe mode - Apple Support
- Make a small test Library on your internal drive with a few pictures in it, set it as the System Library, and see if it begins to sync. You'll need to stop it before it downloads your full iCloud Photos!
- Make a new user and see if the same problem recurs with it. This is a bit harder, because a new user can't access a different user's stuff. You would need to move your Library out of your own user's folder up to the general "Users" folder.
The idea is to find out if the problem is with the Library, with your account, or with caches and login items, and stuff like that. One of these steps may fix the problem, but their failure to work also helps figure out what's happening.
Let us know what happens…