I can’t tell you the specific, detailed differences in fingerprinting behavior between the 2 fingerprinting-blocking settings.
But all that aside, I think as long as you have one of the anti-fingerprinting settings enabled, the device’s fingerprint should change between browsing “sessions.” In other words, if you visit Site X; exit the browser and then start it again; and visit Site X again, you should “look like” a different device due to the ‘farbling’ (tweaks various minor responses and characteristics that are generally not visible to the user, but that are consumed by the web server) that Brave applies.