In 2001 he auditioned for the role of Evan Jones on Blue Heelers. He got the role and quit his job as a part-time barman in Sydney, moved from Sydney to Melbourne, and cut his long blonde hair and dyed it brown. His first episode was "Dragged".
In 2002, Daley won the Logie Award for Most Popular New Male Talent.
In 2006, Blue Heelers was axed after a 12-year-run. Davey hosted Channel Seven's Police Files - Unlocked before leaving to work on Sea Patrol. In the 2008 series, Daley played SAS officer Jim Roth on a semi-regular basis. He also portrayed Romeo in the 2012 Australian Science-Fiction Film "Crawlspace". He also had a supporting role in the final season of "Spartacus: War of the Damned".
In 2014, Daley starred in the ABC-TV series Black Box, as Dr. Ian Bickman, chief of neurosurgeon, opposite Kelly Reilly.
In 2017, he joined the cast of the comedy-drama series 800 Words.
