paint the calipers...without removing the wheel? what the what. To properly paint the calipers, you should remove the calipers entirely, clean them, prep and paint.
To answer your question, NO. If you don't remove the calipers entirely, prep them, and paint them properly the paint will fall off very quickly. Our brakes get very hot and if you don't prep them you'll regret it. Also if you paint them with the wheel on you'll get paint on your wheel, and on the rotor causing hot spots to develop on your pads and rotors.
Please don't waste your time, either have a shop do it or just bite the bullet of unpainted calipers.
As others said, take it to a shop and get it done. Either that or buy some caliper covers that are already painted and have someone install them for you. There's a ton of different options for those.
Paint through a spoke, back up or pull forward, apply more paint, back up or pull forward, apply more paint .... repeat until entire caliper has paint covering it... you'll get it done in about 2 hours per wheel, but no guarantees it will look any good....
You can successfully paint the calipers without removing the caliper using the G2 paint system. I used them and my paint was resilient for many years. https://g2usa.com/
-but paint them WITHOUT removing the wheels?? Why would you ever want to do that? 5 Nuts and a jacket stand. You need that much.