I’m probably being very stupid here but should I be able to manually spin the prop shaft (to remove bolts) with the handbrake off, 90 in neural and diff lock on N?
Prop won’t move as both wheels on the ground stop this.
Jack up 1 wheel on the axle your removing the prop from. You should be able to spin the prop round.
The transfer box drives the propshafts (a shaft or both, depending if it is locked or open, or none if in neutral). The propshaft drives the differential, the differential drives the wheels.
To spin a propshaft (therefore) you need to spin a wheel. Std Defender differentials are 'open' so you only need 1 wheel to turn. To do this you need to 'unwieght' it.
Lifting a wheel off the ground unbalances the car.
As @Anaconda says, make sure you chock the the wheels/axle that is still 'weighted" or the car will roll away.