I absolutely adore Civ V, it's one of my top played games of all time (behind SC1, SC2, and now Dominion the card game). I play an Earth style map, large size, with 10-15 other Civs, and just go to town on Science/Industry. I love to play as Babylon, Korea, Egypt, and Poland, and I love to play on Emperor (Difficulty 6). I've tried playing other Civs and on Other difficulties, but this set-up of "strong civ" on level 6 is a nice mixture of ease/challenge. I also love the raging barbarian and random personality settings, they really add an element of chaos and unpredictability to the AI's and the early-mid game expansion and wars.
One of my all-time favorite starts was as Poland with 4 salt resources next to Warsaw. Salt is such a baller resource because it's a luxury good, but it also allows the creation of a mine which boosts production, and production is super key in Civ. I could blast out wonders and the cutting-edge buildings in 5-10 turns, and my tech lead meant almost none of the wonders were unavailable. Don't you just love having 20 wonders in your capital by the end?