Main (High) beam: you have to have it set to Auto and there is an additional step for auto high beam that I'm blanking on. You have to then leave the stalk in the forward (high beam) position. What may be tripping you up, though, is that the car won't put the high beam on below, IIRC, 25MPH.
Defogger: assuming you have a heat pump, you need to select either heat OR A/C with the defog/defrost vent position. Both come on by default, but this requires the resistance heater to provide the heat while the heat pump provides the A/C, and the resistance heater draws a LOT of power. If no heat pump, then A/C uses much less energy than heat, if the ambient temp allows it.
Scarlet Ember 2018 Leaf SL W/ Pro Pilot
2009 Vectrix VX-1 W/18 Leaf modules, & 3 EZIP E-bicycles.
BAFX OBDII Dongle
PLEASE don't PM me with Leaf questions. Just post in the topic that seems most appropriate.