If you’re referring to the Gamut Volume calculation in the Profile Inspector, you can get more information on that in the ColorWiki:
colorwiki.com/wiki/ColorThin … r_Profiles
The “units” represented by the gamut volume are cubic Lab values.
You would not be able to acheive more volume, or a larger gamut, merely by adding more patches to a profiling chart. That would be something like adding more lines on a ruler - it won’t make the ruler any longer.
Between two gamuts, the one with the larger gamut volume is by definition a larger gamut. However the larger gamut may or may not be encompassing the smaller gamut. That’s why you have the Grapher in ColorThink! You can see exactly where the two gamuts differ, and if one “pokes out” in some areas where the other doesn’t.
Keep asking your questions. I love to answer ColorThink questions!