Sorry using PVA over a painted substrate is a not advisable at all. Unless the surface is chalky this will help bind the surface. If the painted surface of the wall is flaking, simply scrape the flaking paint from the wall. If the plaster is showing after scraping flaking paint, simply coat with a 1 part PVA and 5 part water mix to bare plaster then face fill with quality filler (toupret interior). The problem you will find painting over a PVA sealed painted surface is slipping of the paint or a crocodile effect. If the wall is an exterior wall use a good quality penetrating sealer followed by two coats of masonary paint.