I recently used white PVC 1/4-round nailed to the (white-painted) wooden baseboard of an interior room, to cover the expansion gap of some newly-installed floating engineered flooring. Thus, I can't speak to PVC's paint-ability or long-term durability. As for cutting & nailing...
I cut it at a 45-degree angle on a power-mitre (chop) saw, with no problems. There was some very occasional fraying at the cut, easily trimmed with a utility knife.
The PVC feels softer / more pliable than the oak 1/4-round I used in another room. I had no fears at all about nails splitting the PVC; it seems like you'd have to use absurdly over-sized nails to cause it to split.
Overall, I would go with wood if I had to paint or stain it to match. However, I've been very happy with the look and performance of the white PVC along my white baseboard.