Can you stucco over paint?
We have a home that has stucco. Stucco is actually applied to chicken wire that is nailed to the walls. It is not applied directly to the wall. However, I believe there may be a faux (fake) stucco that you could apply to the wall. But true stucco is a several step process that applies to the wire. This site sort of describes it. www.thoughtco.com/
Are you wanting to stucco over an outside concrete block wall?
This will be an intensive and expensive undertaking so I would suggest you get an estimate from a contractor showing as much of the detailed steps they will give/show you. This will give you some ideas about real cost and what may be involved. Be sure to ask how long their work will be guaranteed and estimate of life of the stucco.
www.stucconews.net/
I would think you need to make sure the painted surface is sanded and rough enough
You have to make sure there is no peeling paint. There is a bonding agent that needs to be applied before the stucco.
Stucco can't be applied to a smooth surface or else it will crumble off. It is essentially like plaster. The chicken wire idea is correct.