I have had good success using several different makes of rattle cans by carefully masking the tyres while still inflated. Use short, two inch or so, lengths of masking tape . It will slide down between rim and tyre enough to allow satisfactory painting of the rim edge. I mask and spray both sides. Do not forget to mask the valve.
If I am replacing the tyre, I have the wheel professionally de-rusted, stripped and primered, then use rattle cans for a finish coat.
I use the same technique on all my painted steel wheels, except the MG which has a fancy (Rostyle?) finish.
Looks as good as powder coat from six feet away and I never worry about the wheels getting chipped or otherwise damaged while driving on gravel roads.