The 27-year-old came into the game as the Isthmian Premier League side's top scorer this season with 14 goals in all competitions and he proved his prowess with two instinctive goals on the artificial pitch at the Gallagher Stadium.
A 0-0 draw at the Lamex Stadium had forced a replay, but Collin struck just 68 seconds into the match to turn home a rebound after Chris Day had parried Jay May's shot into his path, and the hosts comfortably held on to half-time.
Stevenage are 60 places above Maidstone in the English football pyramid and showed their superior class to level shortly after the interval through Darius Charles' classy first-time volley.
But Collin proved the hero, leaping highest to plant a firm header beyond Day's grasp and take Maidstone to the second round of the Cup for the first time since the club we re-formed in 1992.
Awaiting the Kent side in the second round are Conference outfit Wrexham - who will host the seventh-tier side on December 6.