Here is the NRAO's page about the NRQZ. In short, for anyone more than 10 miles from Green Bank the limits aren't very restrictive, but you are subject to coordination. Coordination means that you have to submit fairly detailed information about any station you build to the NRAO, and not operate until they approve (or at least until 20 days pass without them objecting). Any changes to your station will have to be re-approved.
The rest of this is a bit of hearsay, as I haven't been through the process myself (I've visited the NRQZ, and done my research, but didn't do anything that actually required approval). But from what I understand, they're happy to receive emails, and amateur radio is generally not a major problem for them, particularly if you're on the edges of the zone and not within line-of-sight. If you give them a sketch of what you're planning (e.g. amateur frequencies, 100W SSB/CW/FSK, into such and such an antenna, located in North Garden), they will probably be able to conclude very quickly that you're no problem and that they don't need incredible detail. They should be able to guide you on the quickest way to fill out an application so that they can send you a letter allowing you to operate.