Hi
Im probably too late to assist now!
I had this same issue on my build.
If you have to maintain the 100mm cavity then you need to pick out the most protruding "wonky" bit and use this as the datum for the internal blockwork.
On mine the protruding area was most prominent at wall plate , so I used a plumb line from this point and projected it down to the foundation. measure the 100mm cavity from this point. Its you decision if you want top make the internal square or not.
I had a 50 mm cavity on mine, with a leaning wall of 125mm. So at worst case I had a 175mm cavity. I drilled holes on the existing wall and used epoxy resin to set in wall ties. The ties I had made bespoke, in 3 sizes 150mm, 225mm and 300mm, with a wavy tail on one end to epoxy into the hole and a "kite" shape at the other to fit in the new mortar joint.
Hope this helps ?