Thank you BoltBait.
When I use other software (Newsoft CD Labler, it came with the printer, but is otherwise terrible, which is why I am trying to get Paint.net to work), it is able to print to the very edge of the CD and beyond.
Paint.net seems to be printing a slightly cropped square. It is able to print to the edge on the corners, but not on the 'flat' sides. Is there any way to edit what Paint.net CD print settings?
Attached you can see a picture I drew as an example. Than the printer settings (I have tried with, and without, "fit picture to frame"), and then the resultant CD. You can see that it over spays the corners and the center, but doesn't even get to the 'sides'. It really looks like it is just printing a square...
I can use template lines to crop off the parts I don't want (the corners, and the center), but I can't get it to actually print to the edge of the sides.