I did use just the spray can - bought a "kit" online that had 4 cans and some precleaner. I used about 2 cans to get a good coat.
We have both summer and winter tires, so I tried to do these while the winters were still on so I could take my time. I don't have a garage and spray painting is forbidden in the basement, so I worked in my shed. Unfortunately the nice warm day we had was very humid, and the temperature went up fast - so cold rims in warm humid air picked up a lot of condensation. I actually had better luck starting out at night. I still ended up with some bubbling/lift in the inset portions of the spokes. If I have major peeling problems I will just have to suck it up and peel and start over again - luckily I know the two cans I have remaining should just do the job, if I prep better next time. I did end up taping the inside of the rim and the tires, because I had a roll of Harbor Freight cheap-and-staining painters tape to get rid of.
Wheels were a good place to start - it's a small enough job, and it's low so you really only see it from far away. My actual first test was on her old car - I threw a red stripe across the hood, to see how well it held on in the worst conditions (directly in the wind, with two exposed edges). Seems to stick pretty well so far.