^ At £55 for a big tin and using an average 50ml per tankful, it's costing you a fraction over a penny a litre on your fuel costs. Buy Shell Vpower over standard diesel and the difference is 12-14p a litre.
Vpower diesel is less potent than standard diesel, it is 8% less calorific as the average hydrocarbon chain length is shorter due to the natural gas synthesised portion. It is definitely purer and you get fewer regens when using it, but your mpg will be noticeably down on the standard stuff. Its only advantage is cleaning up a dirty engine, that's where people will see an improvement in their car. I used the stuff for the first 4 tankfuls on my GTD and ditched it, seeing an improvement when I did.
Cetane number for diesel fuel is optimum at around 55, Millers helps your fuel get there. There's a fine line on fuel volatility - petrol cars are trying to be a little more like diesel with higher compression ratios, higher Cetane makes the diesel to be a bit more volatile, combusting slightly earlier for a more complete (and cleaner) burn with better response.