Hey steadman: I've been using VBL's for years and always use them for really cold outings. In no particular order, here's what I've found:
1) They are particularly useful for a person who tends to perspire a lot into his/her socks, and/or for super cold conditions. If your socks rarely get damp in the winter, or if you tend to go out only on the "warm" winter days (where the air temp is, say, 5 degrees or better? Just an arbitrary threshold...) then VBL's may be unnecessary.
2) Use: You slip the VBL sock over a bare foot or, I think more commonly, over a thin liner sock then put your insulating sock over that. The theory is that once your skin reaches a certain point of saturation your body's perspiration mechanism stops producing moisture. That seems to be the case, because when I use them my liners are damp, not soaked. Not even close. But my insulating sock is bone dry, and a dry sock will theoretically keep you toastier longer.
3) A few caveats: You
must use them with really good insulation. With only a VBL,a liner and a light boot you risk worse damage (frostbite) than with no VBL at all (trust me on this... I have personal experience

). And again, if you never get cold feet then you're lucky and are doing something right. But VBL's have been around a long time and IMO are the way to go for either a loooong winter day, esp. if there's some standing around where you're not generating heat (e.g. during a technical section), or where it's a multi-day/overnight thing and the thought of putting on damp boots or liners in the morning makes you want to wretch.
4) As for gear, I use thin Injinji merino wool liner socks. They have individual toes on the socks and I like 'em because I'm not keen on that damp feeling in between the toes I'd get with a VBL and a standard liner sock. I then use Integral Designs VBL's although there are others out there. My insulating socks, fwiw, are either (depending on the air temp & boot) Dahlgren Expedition Alpaca Socks [best thinner winter sock, they fit my snugger La Sportiva Baturas well], or Smartwool Mountaineering Socks [an OK mid thick sock, good with a slightly looser boot] or Climb High Himalayan Socks [hands down the best winter sock made, but I save those for the -20 days].
As always, solely my opinions. Hope that helps.
-Tom