My little brother is not at all confident with the game yet and I want to do some one on one training. Any ideas?

a couple of thoughts try teaming with him PvE or try some straight challenges PVP?

I have tried pvp but him being a lower rank it's a bit difficult for him haha, not too sure on how to get the both of us in the same pve match?

If you team with him, the game should automatically put you in the same pve instance.

And don't forget that the member should match the teamleaders strength/level (there will be a button for that next to the portrait while grouped). Otherwise the mission will be scaled to the highest level in the team - possible resulting in one shot death if a complete rank or more is between the two players.

Worked fine, thanks for the help!