My guess is just how the connectors drew up. Try loosening the connectors a little, bump it square, tighten connectors.

Measure diagonals to check square, do not rely on a square.

Tom

The problem you are always going to have is that it's going to be on wheels, so the front will rack to some degree, each time you push on it.....either way.
I wouldn't necessarily give up on frameless though, just not in-set. If you have an overlay to the drawer fronts, adjust them to be as close as possible to looking even, and let it be.
The only way to get them perfect and stay that way, is to have it "installed" (attached to something solid)

You do have room at the top interior to add triangular gussets.  I would rip 1-1/2” stock at a 45 degree angle to get the triangles. 

Use your diagonal clamp to square the cabinet, and glue and brad nail the long pieces into the upper corners.  That might be sufficient to hold the squareness.

They probably will not interfere with your topmost drawer. 

If you move the bottom slide up about 2” you can do the same at the bottom.  It is likely you will be able to move the slide on the bottom drawer to clear that obstacle. 

Big corner braces would work but would interfere with the drawers.  I think the glued triangular strips will add substantially to the structure because they are going to run the full depth of the cabinet.  You could always add the face frame after, if it does not work. 

Adding the face frame will necessitate remounting the drawer glides. 

If you are planning on the face frame for structure, I would not use pocket screws to assemble the frame.  I would use two 3/8” dowels per corner or a domino.  As mentioned earlier, it has to be securely mounted to the carcase.  Pocket screws would work, but I don’t like the look of exposed pockets.  If it were me, I would definitely use biscuits.  If it is a painted cabinet, you can use confirmats and through screw.  Wood filler or wood plugs would make the installation invisible. 

This has happened to me when I've made cabinet boxes out of cheap builders merchant 18mm plywood.  The back has been square but the front is not.  I tracked it down to the plywood being bowed very slightly and deforming the box.

Regards
Bob

The back is square almost certainly because the back panel is square.  Minus that, it probably would doing the leaning tower of Pizza bit.

Ha Ha...probably right. It actually self corrected a bit yesterday. The amount it is out of square is pretty negligible at this point. 

It ended up squaring up pretty good...  Just have to put a couple of coats of Target on it.