painting/replacing wheel simulator rim liner

Not wheel covers personally but polished aluminum, yes. The method for painting polished aluminum goes something like : Thoroughly clean the aluminum and let dry. Sand the metal surface with coarse-, then fine-grit sandpaper. Apply self-etching primer, let dry, then sand again. Apply paint - multiple coats, and sanding between coats.

Tough to ever go back though once you go through the process if you don't like it or want to sell it in the future.