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So, I play 40k, and have built a chaos marine army I am proud of. But, having only gotten into the hobby with any real seriousness in perhaps the past six months despite futzing with the Dark Vengeance minis for over a year, My minis are at best, on par with the tabletop standard. This is a shame because the real enjoyment I get from GW's products is the challenge that comes with paining them.

What I want to know is if I went and bought a single, big, shiny kit for Warhammer Fantasy,for the sole purpose of seeing just how well I could paint one, which army should I be pointed to?
Do note, that getting a Fantasy Mini will 1) allow me to buy the model purely on looks and the painting/ hobby challenge rather than Futz with optimizing it for actual game play, and 2) prevent me from starting another 40k Army.

Fantasy is full of cool one off figures... I suggest just having a browse and seeing what catches your eye.

You could look to forgeworld for a one off too. They do some purdy monsters

It's down to your taste really but personally I love e bretonnians.
They can field 100 knights that can all be painted differently.
They have a character the Green Knight who is just awesome!

If you're looking for modelling and painting potential, I point you to these four kits:

High Elf Lord:
http://www.games-workshop.com/en-GB/High-Elf-Prince-and-Noble

High Elf Mage:
http://www.games-workshop.com/en-GB/High-Elf-Mage

Empire General:
http://www.games-workshop.com/en-GB/Empire-General

Empire Battle Mages:
http://www.games-workshop.com/en-GB/Empire-Battle-Wizards

All of those are great kits that give you two models with great detail and a metric gakton of options to choose from. If you want something to really go to town on, then look not further.

Other picks:
The Green Knight
http://www.games-workshop.com/en-GB/The-Green-Knight

Archaon:
http://www.games-workshop.com/en-GB/Archaon-The-Everchosen

If you want something BIG and have a good budget: Azhag on Dragon:
http://www.games-workshop.com/en-GB/Azhag-the-Slaughterer

Thank you very much for pointing me in a direction for fancy models. Azhag is tempting but I will likely go for the Empire general.