Hello @FattyBull ,
Much as I explained in your previous thread on masking, polypaint, masking, and polygroups are all highly dependent on the quality of the topology. To get the cleanest results, your topology either needs to be very high resolution (higher than this mesh), or your topology has to be drawn in such a way so that it forms a clean border.
Keep in mind also that polypaint is vertex paint. The color is assigned to a point on the mesh, not to the actual polygon. If points on opposite sides of the polygon have different colors assigned to them, there will be a short transition there between the two colors. If the polygon those mixed points are assigned to is stretched and distorted, or non-square shape, this will cause a jagged bleed in the shape of that topology. A higher resolution mesh will hide this bleed better by virtue of the small size of the polygons. It will be much more apparent on a lower res mesh with much larger polygons.
In the following scenario, you see I have a clean looking polypaint on a fairly low res mesh. This is because the points that I have poly-painted all fall along one edge that forms a clean border with another polygroup. There are polygons that blue-painted verts on one side, and green-painted verts on another, resulting in a short transition between the two colors. Because these polygons are fairly well shaped quads and form a clean edge, the transition is barely perceptible. On either side of that border there are polygons that are not as well-shaped, but they play no role in defining the border.
However, if I change the polygrouping so the green area becomes one loop of polygons larger, now the transition area involves those unevenly shaped polygons, resulting in a jagged edge “bleed” like you have in your example. To correct this I would either need to clean up that topology so the polygons are all better shaped, limit my polypaint to polygons that have clean edge borders, or increase the resolution of the mesh to a degree where the polygons are so small, this bleed is no longer easily seen with the naked eye.
Polypaint performs best on a mesh with evenly distributed quads as close to square shaped as possible. Painting over triangular geometry will create jagged edges, and this effect will be more pronounced the lower res your geometry is.
In some situations, ZRemesher can be used with the “Keep Groups” option to quickly redraw your topology in a more polypaint friendly fashion:
Good luck! 