It's hard to believe now, but back in 1999 Angelina Jolie received only fourth billing for Mike Newell's Pushing Tin. It's even harder to believe that the names in front of her are John Cusack, Billy Bob Thornton and Cate Blanchett. So pervasive is the Angelina Jolie brand in 2010, a brand she's held strong for at least half a decade now, that the suggestion she was ever that girl in the Meat Loaf video seems impossible.

But before '99, the best shot she had of attending the Oscars was on the arm of her father, Jon Voight. When she won the Best Supporting Actress trophy that year for Girl, Interrupted, everything changed. Six months later she'd prove her blockbuster worth on the set of Lara Croft: Tomb Raider and a star would be born.

In the years since she's wowed mainstream and indie audiences to equal measure, with starring roles in the likes of Wanted, Changeling and Mr. & Mrs. Smith. And she's often the best part of duds like Beowulf, Sky Captain and Alexander. But it's the film which hit cinemas just before the Oscar win, Pushing Tin, in which we find Jolie's most engaging performance. It's not a showstopper. It was never going to land her an Oscar. But it's emblematic of the enigmatic Jolie we know today and an example of her power, both with audiences and with men.

For John Cusack's Nick Falzone, Mary Bell was an enigma. A woman that cried over the death of a plant, shared incredibly tantric experiences with her husband Russell (Billy Bob Thornton) and oozed raw sexual energy from every pore. Glen and Les Charles fit her into their darkly comic script by playing to every male fantasy about 'the other woman.' Falzone is happily married, but Mary Bell checks every one of his boxes and an affair soon follows.

But as the story unfolds, and Jolie gets to grips with the conflicts that rage under her character's icy exterior, we fall hook line and sinker in love with her ourselves. We revel in every crisis she refuses to be drawn into with Falzone, batting back his clichéd protestations as though she's swatting flies. "I'm way too sober for this," she deadpans at one point, and in another moment she gives up entirely: "Mr. Falzone, what's the fewest number of words you can use to get out of that door?"

And while she's at her calmest, she's responsible for the revelation that most unhinges Nick Falzone: that she's told her husband of their affair, that they shared a frank and open discussion of their emotions overnight and have emerged closer than they've ever been. Mary Bell is always the calm counterpoint to Nick Falzone, but in this moment they don't even appear to be of the same species.

The film is a time capsule of a certain part of Jolie's life. It was on Pushing Tin that she met her second husband, coincidently also her on-screen spouse Billy Bob Thornton. The stories that followed of their relationship – of vials of blood and fetishistic sexual practices – would echo the kookiness of the character she inhabited here.

But this Angelina Jolie doesn't exist anymore. Her talents have turned in other directions, and her recent performances are informed by a maturity and sense of responsibility that didn't exist back then. That's not to suggest one part of her career is better or worse than the other, but it does mean we'll never get a Mary Bell again.

A moment captured on the eve of a career explosion, a character painted with unspoken depth and intrigue and a woman of immense and beguiling power. Pushing Tin's Mary Bell is unquestionably Angelina Jolie's best role.