For non-comic villains, Victoria from due South would be perfect. From here: Victoria Metcalf was, at one point, the only woman whom Fraser ever loved. She was the getaway driver for a botched bank robbery in which two men died. She fled into the Yukon wilderness where a young Mountie named Benton Fraser tracked her down. They both nearly lost their lives in the process, and a love sprung from that bond, yet in the end his adherence to the law won out and he turned her over to the authorities. She got a lenient sentence for her participation in the crime -- eight years as she turned in evidence. However, upon being released from prison, she sought revenge against Fraser. She burned down his father's cabin, shot Dief, tried to frame Ray for passing stolen money, and framed Fraser for murder. She escaped and is still at large. (1st season - Victoria's Secret)

For "non-comic book women who fight crime without being law enforcement types", I think Mma Ramotswe works, because she uses classic detective work on non-traditional cases. I'd also suggest maybe Wendy Watson from The Middleman.