Pant sample analysis is fairly straightforward in my area of training, which is historic building preservation. You generally try and use something like a pen knife and scrape up a flake of paint . You crack the flake in half and mount a piece of the flake with the freshly broken edge facing up. You then look at the edge under a microscope and look at the individual layers. Be careful, however, because you will also see layers of dirt between layers of paint. You match the color of each layer to a standardized chip from something like The Munsell Book of Color under the same light. This way, you can get a chronological order of paint colors. A tricky part, however, is knowing the chemistry of the paint. Different pigments will color-shift over time. In order to get the color correct, you have to take color-shift into account. Also, some finishes were multi-layered affairs. You don't want to match to the original color only to find out that you matched to the primer and not the finish coat. Faux finishes can be tricky along similar lines.
To many folks, this may be too nit-picky, but I'm glad to see serious consideration being given to an aspect of preservation many would consider mundane, even though it all contributes to the atmosphere we are trying to preserve.
Dave