So many misunderstandings about fuel:
Any improvement from filling up with a different fuel is because it's cold. Cold fuel has a similar affect/benefit as cold air. It's even more noticeable on a port injected engine which has a return line from the fuel rail. This is why diesels have fuel coolers and MK5s switched to a return-less fuel rail.
An engine that meters fuel via air mass can't suddenly improve it's mpg from octane rating or fuel brand. Mpg is directly proportional to the throttle pedal! If the mpg improves, you are driving the car differently, or there is less wind that day, or the air is a bit denser etc etc.
ECUs do not continuously add ignition advance until it hears pinking, therefore 'tunes itself' to the octane. ECUs are set up with the MBT at the factory, for the fuel specified on the filler flap (98 in our case). The ECU can only retard, it cannot 'add' timing on the fly.
Fuel does not 'go off', certainly not within the time frame of a frequently used car. I've had V power sat in a tank for 11 months whilst working on a project car, and it fired up and ran perfectly on 'stale' fuel.
Any sudden change in behavior from switching fuels is likely down to contamination. The Engine/ECU really doesn't care what's in the tank, so long as it meets the minimum RON. It's all pretty much placebo.
I stopped using Momentum 99 back when I had my R32, because it started misfiring pretty much immediately after filling up with it. Never had that before or since with V power.
What I can tell you about V power is it does seem to contain some nice cleansing additives. I did 60K miles in an old project car. Freshly built engine, V power used exclusively. I stripped it down after 60K at everything in the combustion chambers was spotless
These additives make NGK Iridium plugs turn orange!