Yes it can be done in almsot any gtraphics editing prgram, including MS Paint.
I haven't used Paintshop Pr before, but if it has a paths tool, that would be the easiest option. Just make a path around the car, or w/e you want to put on the blank background, convert the path ot selection, invert the selection, delete the background and fill with w/e color you like.
If there is no paths tool, just use the lasso tool.
This can be done easily in GIMP, found here:
http://gimp-win.sourceforge.net/stable.html