These are geared for overclocking and gaming. They just don't have cheesy marketing all over them.
The premium has more power phases than the pro, which makes it better for overclocking. The Deluxe also has more power phases than the pro. The premium is able to do quad SLI and Crossfire with four separate cards, while the Deluxe and Pro can do Quad SLI and Crossfire with two dual GPU cards.
The premium also has more bandwidth in its PCI-E slots. If you put four single GPU cards into the premium, each GPU will run at PCI-E 3.0 X8 which is equivalent to PCI-E 2.0 X16. The Deluxe and Pro only have two slots like this, so if you install two dual GPU cards, each GPU will only run at PCI-E 3.0 X4 which is equivalent to PCI-E 2.0 X8.
There are probably some other small differences as well, but I'd have to look them up. The Premium might actually have more power phases than the Deluxe, but I doubt it. The Premium should have some other higher tier parts that the Deluxe doesn't have though.
Btw, you only need one 8-pin CPU connector to overclock. The only time you would probably even come close to needing the extra 4-pin connector is if you're going to be cooling the CPU with liquid nitrogen.
They also have thunderbolt versions of all their P8Z77-V motherboards, but they cost more. I think the Premium comes stock with that feature though.
Here are some other motherboards I would suggest:
http://www.newegg.com/Product/Product.aspx?Item=N82E16813157322
http://www.newegg.com/Product/Product.aspx?Item=N82E16813128559
I would have to advise you to stay away from MSI, unless they've changed their bios since Z68. I had a Z68A-GD80 that I sent back because it was slowly dying on me. I'm pretty sure I just got a bad board, but their bios just doesn't allow you to overclock very easily in general. If you took the multiplier any higher than 47, it would throttle it back down between 45 and 47. That wasn't just a problem with my board either, because I read a review on the board later, and they all do that. Unless MSI has fixed that problem, I wouldn't buy from them.
Their graphics cards are great, but their motherboards are crap unless they've fixed them.