Based on the clearance between the stock wheels and the Brembo Calipers (I have them myself), Anything stuck over the calipers would rub. On a side note most wheels won't fit as well because the Brembos require 6.8" of backspacing.
As far as painting the Calipers, I used High heat paint on my Thunderbird. Just be careful as it does flake over time so touch ups will be necessary. In my case, I was protecting against rust issues, so I laid a base coat of Enamel paint and then used the high heat paint for the desired color.