The ease of quartering wheels for steam in O can vary tons. Lionel usually used splines which can ease alignments some. Others do too but that isn't always the case. Some are taper pressed. Still others do drop into a "gearbox" chassis with a cover.
Early Lionel open frame was made to be rebuilt. Occasionally with special tools, and much of the work "requiring" an arbor press, with rivet set anvils etc, and in the case of wheels, wheel cups that ensure a quartered, straight press, and other jobs too to be done "100% factory correct" (for collecting reasons this can be important) But a careful mechanic can manage with much less as well if they just operate vs collect, and todays trains differ slightly from what was built postwar .
I sounds like you're trying to get behind spokes... on what engine? Wheel removal may or may not be hard. Or might be worth paying for the service (?)
If it's early spokes, you might not want to paint it. (its a value thing in O ."Everything is fine" if kept original (Me? ....I'd drive a Model T with a hemi backwards in the Baja 500 for fun )
I'd consider masking the wheel back and painting sideways with thin paint that levels well, by brush, pad, swab, taunt string, etc.. through spoke spinning of a brush like an old rotory dial phone might work too.
To spray? I think you nailed it; slow spin and good aim. Mask part of the wheels, but leave a "pie" or two.... or use a masking compound to prevent build up on the spokes before you get to thier topcoats.