I have used copper and shielding paint for both my guitars and for my customer's guitars.
Tape is much more conductive and provides a better shield. However, over time the adhesive degrades and it doesn't always stay where you put it. (This happens over years, usually, as long as the surface was clean when you started.) Even in instances where the adhesive is conductive, I like to solder the overlap to make sure it's conductive for a long time.
Shielding paint requires several layers to become conductive enough to work well. I've measured resistance from a neck pickup cavity to the control cavity at over 100 ohms. That's enough resistance that it will still work, but not 100%.
In applications where it's tough to install copper cleanly, paint might be a less imperfect choice.