Sent into bat, Delhi rode on Samson's 63-ball 102 to notch up 205 for four at the Maharashtra Cricket Association Stadium.
In reply, Pune were all out for 108 in 16.1 overs.
Samson struck eight boundaries and five sixes, while Chris Morris blazed his way to 38 off just nine balls.
Delhi skipper Zaheer Khan picked up 3/20, while leg- spinner Amit Mishra had 3/11.
Delhi Daredevils, thus, recorded their first win in this edition of the T20 league, while RPS won one and lost two in three outings so far.