The grinding isn't the crucial step. It's getting the parts square, and KEEPING them square, as the heat of the weld causes them to warp.
If you have a welding table similar to the picture above, it's not too difficult.
Hypothetically, lets say you were making a 12" x 12" square out of 4 pieces of tubing. Use a carpenters square to mark the desired outline onto the table with a sharpie. (Draw a 1 foot-wide cube on the top of the table).
Now whether you join the ends at 45s, or 90s, it's the same process. Cut everything to length, and lay it out on the table. Now tack all your pieces together. Still look perfect? Good. TACK THEM TO THE TABLE. In 3-4 places on each side of the square. Now weld the hell out of it. Bust the tack welds loose, flip it over, weld the other side, and clean the tack-welds off of your table with a flap disc.
Done.
If you need a piece bigger than you can draw out on your table, it's trickier. Or let's say you're *building* you're table, in which case you probably don't already have one. When I'm working on the floor, I would usually start by getting 2 pieces (both legs cut about 1/2" too long) welded at a perfect 90. Again, tack the hell out of them before welding. 2 tacks isn't really enough.
Then build another, identical L-shaped assembly. *THEN* join the two together. It's much more precise than trying to go around in a circle to each corner, with all the other pieces shifting around.