You should let your dive shop know what the contents are when you bring the tank in, hence the contents label should be left on. Why??? Well here we go:
1) Due to the enriched air content of the tank, if it is being hooked up to a fill whip, and once you crack it open the tank and the pressure in the whips equalizes. There is the possibility for your enriched air to move up into the fill system. If this system is not oxygen cleaned, than it may lead to rupture, fire, or worse. Although this is a slight possibility, it STILL EXISTS. By not notifying the dive shop of your tank(s)' contents, you will be legally responsible for any damage that is incurred.
(Although this isn't related to nitrox fills, it is an interesting account of a tank explosion and the damage that can be done:
http://www.connected.bc.ca/~baquatics/explode.html)
2) All fills that have more than 21% oxygen have to be logged by the shop as enriched air fills and the proper paperwork done. This includes fills which are just air top-ups of a previous enriched air.
Frequently I get a 40% oxygen mix and do some dives with that, I than get it topped up, find out the % O2, calculate my MOD, and get another enriched air dive out of it. I do this until I get under 22% and thus am able to usually get 3 or 4 enriched air dives out of one fill. Each time I make sure to calculate my MOD, my EAD, and my % maximum O2 exposure. I could use my 40% MOD and dive using air tables, but I feel that I am practicing my skills more by planning it out and knowing exactly what is happening with my air, equipment, and how I can adjust my dive profile if an emergency situation arises.