Yeah, there will always be some kind of radius on the inside corners due to the shape of the cutting tool, despite it being a 90 degree angle in the CAD drawing. My early NES boards I think followed a Nintendo board too closely, and it ends up not fitting well because of that. So I've kept tweaking a bit on every new board.
I'm not sure what's up with my pin measurements, my pins are visibly off-center
and I've never moved them because it always works (and seemed to line up visually with other carts). This is what I've got (I'm just skipping over the bigger power pins).
edge to pin 35 center, 5.215mm
edge to pin 2 center, 5.85mm
93.5mm and being centered makes sense, it seems possible that the boards I've compared mine to were within tolerance, rather than being centered. Ultimately, those L-shaped cut-outs are the main part to worry about, and my DXF drawing doesn't even include those (just the bottoms of them).
Board width should be 100mm. I've got 93.6mm + 3.2 + 3.2 = 100mm.