Hi there,
I've had a go at re-spraying various bits of rolling stock and I've got a bit of experience.
The first question is what are you trying to achieve?
If you want as close to real as possible then it's something that, if you haven't done it before, you're going to have to get someone else to do it.
If you want it to be nearly right or you just want to enjoy doing it yourself then there's plenty of things to do. (Personally I liked doing it and really enjoyed figuring it all out and getting results I was happy with.)
Check out the various colours available. You can get some quite good matches with Halfords spray paints and if you are planning to weather / dirty the stock, any subtle variations on colour are quite well hidden.
Better are the Railmatch colours (Google for more details). These come in sprays and pots of paint. They are as close as you'll get to the actual colours but are a bit more expensive.
Spray paints are great if you're starting out and haven't got the airbrush and / or skills to carefully handpaint a wagon.
Do check out what transfers you can use for the fine details.
Finally, your first efforts will *not* be as good as you'd like!
Get a couple of cheap bits of stock from e-bay and practise.
Learn how to apply the paint, how much to put on at one time (less is always better), learn how to apply good quality masking tape and figure out how to support and hold what you're working on.
I enjoy getting the paint job and finish I'm after - it took a few mistakes though!
Good luck,
Mr Toad