I painted some older wheels from my Nissan truck and I really think they turned out nice. It didn't take a lot of prep work either.
1. Clean the wheel to remove all grease rust and dirt. Sandblasting would be ideal but may not be practical. Use a wire brush or better yet, a wire wheel on a drill.
2. I used this as my primer.
http://www.summitracing.com/parts/rll-2494153. I used this paint.
http://www.summitracing.com/parts/rll-248930 It gives a finish similar that looks like brushed aluminum. I'd say that from a distance of 6 feet you would think they were alloy wheels and not painted steel. This paint comes in different colors but not any primary colors like red or blue. For primary colors, you could use any high temp engine paint or brake caliper paint and then clear coat with this if you wanted.
http://www.summitracing.com/parts/rll-248929Red =
http://www.summitracing.com/parts/rll-248962/overview/Another brand might work well too. =
http://www.summitracing.com/parts/vht-sp186All this stuff is available at your local auto parts store.
