Ever notice one of the first places you see rust on wheels is the crevice where the center joins up with the rim because the sprayed paint doesn't get in the crack.
Before I spray my wheels I thin the paint a little and paint that crevice with a brush letting it run into the crack, where sprayed paint can't get to very well. Look for drips out the back side and wipe off.
If done right with a small brush any brush marks left will be covered when you top coat the wheel.
Dan