XRF works well on heavy elements, like gold, lead etc, less well on lighter elements like aluminium, and virtually not at all on the super-lightweight elements like carbon, nitrogen and oxygen, that paper is made of. So unless this "Luminus substrate" incorporates heavy metals in the plastic or paper layers, it's unlikely to be useful for paper money.
More useful would be infrared analysis. ATR-FT-IR (Attenuated Total Reflection Fourier Transform Infrared Spectroscopy) is a non-destructive technique which should be able to distinguish between a piece of paper and a piece of plastic coated in paper.
Don't say "infinitely" when you mean "very"; otherwise, you'll have no word left when you want to talk about something really infinite. - C. S. Lewis