She has appeared in a number of feature films, including Love Serenade, Blackrock, Cut, City Loop, Angst, The Illustrated Family Doctor and Ghost Rider, and is well known for her role of Becky Howard in the Australian TV drama series McLeod's Daughters.

A year later she reappeared in another episode, when her father nominated her to fill in for a role when the girl who was booked for the job refused as the character was required to be submerged in a swamp.

Small parts in a string of other popular Australian TV shows, including Water Rats and Murder Call, followed; she played the role of Gerry Davis in the highly acclaimed Wildside, alongside Aaron Pedersen, Rachel Blake and Tony Martin.

Napier then appeared in Stingers (with Peter Phelps) and City Loop before landing the lead role of Raffy in Mushroom Pictures' film Cut.

The thriller Savages Crossing was released in 2010 and saw Napier star in an ensemble cast of other Australian favourites including John Jarratt, Craig McLachlan, Sacha Horler and Chris Haywood.

In 2021 Napier appeared in a small role in Moon Rock For Monday,[3] an AACTA-nominated feature film directed by Kurt Martin.