Couple things, paints, especially done at home are always going to chip off and wear badly. The only way around this is to use automotive paints, and follow VERY strict prep, application, and post application regimen. The reason is because 90% of a quality look of a paint job comes from the prep work. With painting plastics, you do not have the option to cure in an oven which automotive paints are designed for. After spraying, it may feel dry and cured, but if it still smells like paint, then it isn't done curing yet. The smell means there are still solvents in the paint evaporating.
Couple things on plastics. ABS shines much faster than PBT. Most of this has to do with chemical makeup of the oils in your fingers and the make up of ABS plastics used in caps, and how those two interact. Also, there hasn't been any way to favorably alter the texture of caps to my knowledge post shine.
By all means experiment away, just try not to get discouraged and please experiment on spare caps.