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The Proton Drive Photo Backup is, if I understand correctly, a pure backup, no sync. When activated, all photos on your GrapheneOS device (or the photos in folders you assign to Proton Drive via storage scopes) are backed up to the cloud. If you delete a photo on your phone, it will not be removed from Proton Drive and vice versa.
However, Proton Drive offers an option of creating synchronized folders. The folders to be synchronized are set up on the computer (Windows or macOS, via the corresponding Proton app. Once the folders to be synchronized have been created, you also can find them in the Proton Drive app on your Pixel device in the “Computers” tab>“Name of your computer”. If you add or remove files here, they will also be removed from Proton Drive and other connected devices.
I am currently not aware of any way to manually or automatically move photos that are loaded into Proton Drive using the automatic backup to a folder that is synced (though i have to admit that I haven't really looked into this, as the backup as it works, is perfectly fine for me personally - i synchronize my files locally with Synthing, Proton's automatic photo backup is just a nice additional feature for me in case I lose my phone traveling, eg.).