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Now that I've finally mastered NMM I'm looking to paint some DV models in the colours of the black legion. And I want to paint the models completely in NMM, including the black. So my question is how bright should my final highlight be? Administratum grey? Brighter?

It depends. If you're aiming for a metal, in the end, you'll have to use white, at least in an small section, to make it look realistic. If you want to "play secure" and do it in a more GW style (as duncan tutorials, for example) use administratorum grey.

"Realistic" black metal reference (with white)
https://s-media-cache-ak0.pinimg.com/736x/3a/27/92/3a27922f315053f17bc824e1ff943497.jpg
http://ep.yimg.com/ca/I/yhst-87491460501412_2269_120814189.gif

GW one:
https://www.youtube.com/watch?v=783slFWP61M


*Edit: References added.

This is a pretty fantastic guide on shiny black NMM, using only 3 paints:
http://flameonminiatures.blogspot.co.uk/2014/01/black-color-painting-tutorial.html