Sims, 34, has captained her state New South Wales as well as her country, and is now classed as 'semi-professional'.
The deal coincides with the proposed launch of an Australian women's competition in 2017, and the World Cup to run alongside the men's tournament.
"It's a hugely exciting moment," Sims said. "I feel very privileged."
Sims is the sister of Warrington prop Ashton Sims and Newcastle Knights duo Tariq and Korbin Sims.
"It's so exciting to be in a position where we'll be considered semi-professional and to be paid to play the game that we love," she added.
Australia Jillaroos captain Ruan Sims has signed the first paid contract in women's rugby league, a one-year deal with NRL side Cronulla Sharks.