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It depends on the type of paint used in the existing painting. If it is an oil painting, you will need to use oil based paint. If it is a water based medium, like acrylic, use a water based paint. Gesso will work well for this. It is inexpensive, opaque and will help level the texture of the existing painting. You may want to lightly sand the painting before painting over.
If the stucco has never been painted, a new color coat can be put over the old finish by using an acrylic in the mortar like flex-con. Our formula generally is using a half and half mixture of acrylic bonding admixture with water and mixing with the dry finish coat mix. There are other methods, but this is the simplest.