She is known for her roles as Rachel Bradley in the British comedy drama Cold Feet (1997–2003) and Emily Waltham in the American sitcom Friends (1998–1999).

Baxendale's early stage credits include The Soldiers at Glasgow's Citizens Theatre, which earned her a 1993 Ian Charleson Award nomination.

Her other television credits include Cardiac Arrest (1994–1996), An Unsuitable Job for a Woman (1997–1999), Adrian Mole: The Cappuccino Years (2001), Cuckoo (2012–2019) and Noughts + Crosses (2020).

She wanted to be a ballet dancer and trained at the Elmhurst School for Dance, until dropping out aged 17 in favour of an acting career.

Via her work at Glasgow Citizens' Theatre, Baxendale was cast in hospital TV series Cardiac Arrest, though it was not her first television role.

"[3] Aged 27 Baxendale was cast in a recurring role in Friends as Ross Geller's girlfriend, wife and ultimately ex-wife Emily Waltham.

She played Pandora Braithwaite in Adrian Mole: The Cappuccino Years in 2001 and "Maggie" in the multiple award-winning Bolse Vita.

In January 2011, she co-starred with Trevor Eve in the three-part ITV drama Kidnap and Ransom, filmed on location in South Africa.

Baxendale starred as Christine in Patrick Marber's After Miss Julie, and in 2005 appeared as Romy, the title role in The Woman Before at the Royal Court alongside Nigel Lindsay, Saskia Reeves, Tom Riley and Georgia Taylor.