I haven't done this, but I'm not sure why it wouldn't work: First, create a new Apple ID -- you get 5 GB of iCloud storage, and this will keep you from messing up your iCloud Photos on your current ID.
Then make a small Library, a few hundred pictures, maybe, and make it your system Library for that account. Once it is populated into iCloud, switch iCloud off on that Library and create another one with the same name on an external library and make it your System Library on this new account. Photos should make this identical to the first Library, with the same few hundred pictures. Maybe add a few new pictures. Then switch back, making the original one your System Library, again, and turning on iCloud, and see if you get the new pictures in this Library, too.
I think that you can switch back and forth at will, and Photos will keep making each one identical to the iCloud version. If this is with a new ID, then you won't have anything to lose with the experiment.