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I've started using some rollers I found on ebay to make scenic bases, for those that don't know what Im talking about http://www.ebay.com/itm/Rolling-Pin-small-COBBLESTONE-Texture-Create-your-bases-Warhammer-Bolt-Action/282173038214?ssPageName=STRK%3AMEBIDX%3AIT&_trksid=p2060353.m1438.l2649 is one of the versions the seller has.

I've done a few bases for far, and they have worked pretty well, I spread some greenstuff on the base, roll the rolling pin over it and then push the mini into the greenstuff just enough to stick and hold, but not so much it distorts the putty. The problem I'm having is painting the base. I'd like to make the base, paint it, then put the mini onto the completed base, so I'm wondering if anyone has any experience in attaching minis to hardened greenstuff, and what's the best 'glue' to use.

Yup.
No problem at all.
Just use superglue.
You may want to mix your greenstuff quite hard ie use more blue.

Same as above. More blue makes it harder. Superglue should be fine. Also, if you press the mini in and therefore have a "footprint" you can pin him if worried. Just drill into foot and base. 1/16th bit (found at any hardware store), and large paperclips. Hey how about a picture or two to show what you end up with?

This is made using the 'Frozen' rolling pin from the same seller.

I use Milliput when I make bases with the Green Stuff World rollers, put some water/vaseline on the mini's feet, push them in (if you want the feet sunk in, otherwise leave it) and then once it's cured either just superglue it in place or for some models I drill through the milliput & base, insert a pin and then pin the model through the foot