Hi Paul,
I would start by saying that the sizing of the relief is a very serious undertaking, and any sizing that you do should be confirmed with someone who has the experience that you currently do not have. The point to remember is that it is a life safety device and you should always treat the sizing and specification with the utmost reverence.
Now, having said that, the starting point is with our system review and defining what you are protecting and what is the limiting factor, and what is the worst case. If it is a vessel, if it is a pump, if it is a boiler, thermal expansion in piping, exothermic reactions, and so forth. There are hundreds of potential cases spanning all of the various industries in which pressure saftey valves are employed. You have to identify your case, and then have an understanding of the applicable codes regarding saftey valves. NFPA, API, ASME are the big three when it comes to relief devices. All of the codes have very specific sections on the calculation methods.
Go out and search around under these three codes, and you will find the applicable sections (I would give them to you, but I'm on the road this week). Perhaps someone else can direct Paul to the specifics, but again it does depend upon your application and worst case senerio.
Hope that this was of some help.
Best Regards,
TSeener