Orochimaru has already beat Jiraiya 2 to 0. Plus, I'm gonna use some A>B>C logic here that can be applied..
Orochimaru fought head on [for entertainment] against 4-Tailed Cloaked Naruto with no Jutsu, suffering from necrosis still and a fatal fever..... Also with no preparation time.
Jiraiya fought and tried to control Naruto at his 4-Tailed Cloak state and was almost killed, with preparation and full knowledge of Naruto's wild abilities and had countermeasures in place.
Given that, if they both were at 100%, I'd give it to Orochimaru, countless experimentation on himself plus the Immortality Jutsu gives him an upper hand over Jiraiya who unlike Tsunade & Orochimaru both has no healing capabilities.