I was afraid you'd say something like that.
I think I have made things worse tonight, as in a fit of desperation, I decided to toil through my registry and delete any keys with "paint.NET" in them - in an attempt to completely clean my system of any old, out of date Paint.NET related links which could be causing the FileNotFound error. Upon rebooting my laptop, ATI Catalyst crashes repeatedly (hundreds of times in a matter of minutes) with a clr20r3 error - making it almost impossible to do anything. I have a registry backup somewhere in my documents, so I will try loading that up tomorrow.