If you have bare patches of alloy that you want to paint over, then you must etch prime! then followed by 3/4 light coats of white primer (this is the best colour primer to use if you're going to cover with silver) when selecting a silver to paint your wheels, I would try to avoid any silver that has pearlescent tinter present, this could make your wheels look a little strange, and you wouldnt know why! Mercedes "Brilliant silver" code 744, is an excellent choice, being clean and bright, and no pearl! then 2/3 coats of lacquer to finish.
Halfords can mix any colours, including VW colours!....
Tom