If you have profiled skirting...
I masking tape the floor on the internal and external corners that the skirting boards will follow in this area.
With an off cut, say 300mm long, cut square edge, I put the skirting against the wall and slide it into the internal corner and mark the front path of the board onto the masking tape, do this for the left and right handside of both internal corners.
You'll see that the pencil lines cross each other, this cross point helps you find the true angle for each piece.
Put the off cut back on the left side of the left internal corner, slide it back into the corner until it stops, on the bottom face edge of the skirting mark the point where the lines cross.
With a sliding bevel marry the back corner of the skirting to this mark from underneath, this will tell you the exact angle for this piece and all subsequent boards using the same method.
If you also trace the front line of the skirting around the external corners it not only gives you those angles it also tells you how long each piece of skirting should be when you measure the cross points on the masking tape.
Test all internal mitres prior to doing final full length cuts.
Patience is required.