There's some good quality caliper paint online. But I would say pay to have someone do it. I had mine done and it was pretty inexpensive but I know it was done well. The rims I can't really help you on, but my guy that paints my car had offered to do it, for a good deal too, just not my style. I'd imagine they are difficult upkeep versus buying black rims. Definitely a fan of painted calipers tho!
Have you ever noticed that anybody driving slower than you is an idiot, and anyone going faster than you is a maniac?