XRF Handheld Analyzers 
There are more than one manufacturer of this nifty piece of technology. The only sites that I have had the time to check out are InnovX and Niton.
The InnovX site, in my opinion, does a better job of explaining the technology and the handheld analyzer itself. Read what they say about CPSIA and their analyzer.
They have some great videos showing it in use testing toys and other products. Niton offers webinars about their analyzer.
From what I understand, Niton offers a silver covering that goes over the machine and your hand, should you be concerned about x-ray exposure. I think the InnovX machine is made differently, because they state on their site that there is no exposure behind the machine, and the only exposure possible in front of it is where the beam is actually hitting. But, you have to check that all out yourself.
Read what The Smart Mama has to say about xrf and CPSIA here. Yes, she does offer testing, but she is in California and hasn't paid me for any plug here!
XRF Testing
I have spoken with several people who have been using these handheld analyzers to test both toys and clothing. Not only those that have started their own testing services a few years ago, but those that work for nonprofit kid's safety groups that have used them when they have sponsored Safe Toy events.
They say that after several hours of training, they are fairly easy to calibrate and use. They weigh, on average, about 3.5 or 4 pounds, from what I have read. One of the manufacturers has, according to them, produced a Standard Operating Procedure Manual on how to use their analyzer to test clothing and toys properly and how to calibrate it. (That did not seem to be difficult at all) For instance, when testing clothing, as I understand it, you must not only test each type of fabric on the clothing, but also each zipper, button, embellishments, snap etc.
Just to provide a rough estimate for those who have been interested, the average rate of tests that those I spoke to are normally able to accomplish is between 15 and 40 per hour. Clothing normally requires 1-6 tests on average, per piece.
Some states require people that use the analyzer to be licensed. Some require just the analyzer to be licensed. Some have no requirements for it's use.
THE TESTING PROCEDURE/DATA COLLECTED
Some people that have testing services, like two men in Washington State, developed their own program for their analyzer to more easily capture information. Most I have spoken to all capture the same information when testing items.
They take a photo of the item. In the case of clothing, they take a photo of the item and the tag with with RN number on it. They enter a description of what they are testing (what location) and then perform the test. The machine does the analysis and either says pass or fail. This is all saved in a computer program and reports are printed out.