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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.
Acrylic on top of wet watercolor. By painting with acrylic on top of still-wet watercolor, you can attain some very pretty, sheer-looking results. For instance, on the above image, white acrylic paint is applied over a still-wet wash of blue watercolor paint.