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Decimating only removes verticies.( subdivide and subsurf can add.)
You don't need to decimate or in any way remove verticies to vertex paint. Vertex painting is the easiest, but it attaches a color value to each vertice, so the fewer verticies you have, the less contrast you can get over an area. Adding verticies( by selecting All and subdivinding) gives better control, but new verts don't come assigned to a vertice group.
In vers 1.3 of the Blendtut in chapter 2 I explained how to assign verticies into material groups. It's not as easy, but It gives better and more stable results.
Decimating only removes verticies.( subdivide and subsurf can add.)
You don't need to decimate or in any way remove verticies to vertex paint. Vertex painting is the easiest, but it attaches a color value to each vertice, so the fewer verticies you have, the less contrast you can get over an area. Adding verticies( by selecting All and subdivinding) gives better control, but new verts don't come assigned to a vertice group.

In vers 1.3 of the Blendtut in chapter 2 I explained how to assign verticies into material groups. It's not as easy, but It gives better and more stable results.