Hi Kane,
The quality of these vinyl coverings varies a bit among different manufacturers so it's hard to say.
What species will this be for? If it's something that scratches a lot or needs very high humidity you'll probably want to cover it. It would probably be fine for a leopard gecko.
Getting a paint to stick can be very tricky. There are flash primers that will sometime help but they don't always apply well without a sprayer.
For something like a monitor I would apply Fiberglass Reinforced Panel, sometimes called FRP board. It is that hard, textured plastic often found on restroom walls. If you go and ask for FRP board some places will confuse it with "Fire Resistant Panel" -- not always the same thing.
For a high humidity snake you might be able to get away with applying a rubberized contact paper and then caulking the edges with aquarium sealant. This will be A LOT easier if you can disassemble the unit and apply the paper to the individual pieces.
For more on this follow the link below. It's worth navigating through other parts of the site for even more information.
contact paper