Top 10 units for a PSY Team (in no particular order).
Captain Ability: 2X ATK & 2X HP to PSY units.
Special: All orbs into either PSY or RCV.
HP: 2852. ATK: 1220. RCV: 225.
Garp's greatness lies in his awesome special. He can easily help your team with orbs, whether you need more power or more healing, he can do either. Garp is definitely a powerful captain for PSY Teams.
Captain Ability: 2.5X ATK to PSY units.
Special: 15X PSY damage to all enemies.
HP: 2118. ATK: 990. RCV: 417.
Shanks has a powerful captain ability, but his special kind of sucks... and his stats aren't the greatest either; however, Shanks can still captain a pretty powerful PSY Team.