Make sure to test a piece of the vinyl with the paint you use. It would suck for the thinner used in the paint swell the vinyl and dissolve the glue.
The vinyl that commercial lettering works good, and you don't need high temperature paint for the engine or the valve covers.
Bumper sticker vinyl works the best.
As with any vinyl lettering material, you may have some glue stick to the surface, but you can rub it off with your finger when the paint is dry.
Frank Cox
Cox Custom Cars