This seems pretty bleak. To a hardcore skeptic, pretty much any science could be ruled "speculative at best". Is there a better method of testing available? This is far from terrible and "nothing" seems to be the alternative. Is any other person or organization out there checking steel claims for EDC knives?
As far as trying to trick the testing, that seems a little far-fetched. Imagine what would actually be involved in finding alloys to closely match the Cr, Mo, V, etc. of a popular blade steel, just in case of the one guy doing XRF testing, and machining that alloy into a passable product. The companies putting false steel stamps on knives seem unlikely to pursue such an effort. Generally, they are going to do what they can to get their product to market and make a sale as cost-effectively as possible.
A common tactic in the world of fake steel stamps is the rebranding of an existing product. For instance, Company X makes a cheap but functional knife in 3Cr13, 5Cr15, or 8Cr13 on the high end. Company Y buys them in bulk, stamps them with whatever logo and a steel stamp that they think will sell it in the West, and charges a substantial mark-up on AliExpress, Amazon, eBay, etc. Despite a few recent developments, Eafengrow is probably the most well-known example of a Company Y in the current market.