I had this debate at work, and as they pay my fuel expenses I decided to test this. I ride a motorbike so perhaps not too appropriate but the results probably translate to cars easily enough.
I fill up at a shell garage once a day, so I switched from using their standard unleaded to their vpower (?) stuff for two weeks.
Normally I get about 52 MPG, and I travel on average about 98 miles per day (week days). The first thing I noticed was a slight and I mean slight increase in acceleration, but the MPG hardly changed at all, at best an extra 2 MPG.
So no major gains with the Super Unleaded at shell.
BUT... I started filling up at a garage just outside Bristol on the A38, some little petrol provider, but the fuel resulted in a pretty good increase in performance and similar MPG, next time I'm there I'll write down the name of oil company providing the fuel, it's pretty cheap too. (NB at this garage it was also their super unleaded stuff)
David