Singles, your probably not going to be able to reach it, and correct me people if I am wrong, but I can't think of why you would need to, shouldn't be shutting down your only air source underwater.
As for doubles, when I went to doubles and my tec training this was my greatest concern, I had practiced reaching the valves and couldn't get at them. Then my instructor taught be, pretty much spot on what Andy ( Devondiver) just said above and first shot I had them. I was over reaching, reaching so far out I was passing the valve. Head up, slide hand up past ear and you should have them. I have sometimes given my shoulders a little shrug to help push the tanks up my back.