The 53-year-old, who scored 42 goals in 134 appearances for the Pilgrims during two spells in the 1990s, was at training for the first time on Thursday evening and will supplement United's existing staff which contains Greene and assistant manager Martyn Bunce.
Cavell lined up alongside Greene during their playing days at Dagenham and Redbridge and is expected to be in the dugout for the first time when United visit Nuneaton Town on Saturday.
He is currently working within the Centre of Excellence coaching set-up at Doncaster Rovers.