//.just how to get the angle!//
The angle, as you call it, is simply the extension of the two surfaces, meeting at 90 degrees. so if you 'overfill' so the filler stands proud of the corner you want, as I said above, you use something like a surform tool flat against each face to file down and create the corner.
If you haven't got a surform tool, glue some coarse sandpaper to a piece of straight wood and use that.
We have no idea of what size this job is though, unfortunately