What is the purpose of the Default Folder? The setup documentation did not say, nor did I find any instruction on what to do for initial setup in my case from one folder on my computer to a folder on an HDD attached to the same computer.
Just saves a new user a little bit of time setting up the first folder. My guess is that many users don’t use it. If you likewise don’t need it, it can be deleted along with the default ~/Sync
directory that’s created.
It’s not an intended use-case because Syncthing expects to talk to another instance of Syncthing, normally on another device.
It’s possible to do what you’re asking by running multiple Syncthing instances. You’ll need to customize the network port assignments to avoid conflicts plus other tweaks, but it’s doable.
However, if all you want is to sync two folders on the same computer, there are better options/tools for that.
As someone actually doing some synchronization between multiple instances of syncthing running on the same host, I agree. I would highly recommend against it, unless really required. If still interested, be prepared to fully ditch the gui and create those configuration files by handcrafting xml as attention to detail becomes necessary.
Please feel free to describe your usecase.

from one folder on my computer to a folder on an HDD attached to the same computer
Highly recommend FreeFileSync for this use case.