2014 freelander2

I had new rear discs and pads fitted last year and have noticed the the hubs have started to rust, is there any way I can Jack up the car and still be able to rotate the hubs so I can paint them

Not sure where you trying to paint but there are jacking points under the car just behind the sills, front and rear.
I think there are markings pressed into the sill pointing to them, but if you look underneath you will see what I can best describe as large 'bumps' with circular holes protruding from the floor pan.
Jack up slowly and listen for any loud creaks or flexing !
If unsure try going to a tyre repair place and see what they use ?

Most rotor manufacturers paint the bells these days, meaning they stay looking rust free for years.

At to the question.
Yes there is.
The vehicle needs to be on level ground, you'll need to chock the front wheels, and put it in 1st or reverse for a manual, or PARK for an auto.

Crack off the wheel nuts ½ a turn on the wheels you want to remove.
Then lift the corner you'll be painting, and remove the wheel.
You can turn the hub by releasing the parking brake, as the vehicle shouldn't move if it's in gear with the wheels chocked.
Only paint the visible part of the rotor bell, as the wheels need to go against steel, not paint.
Otherwise it's a pretty simple operation.