Get the pencil out of the black box by pressing the left arrow key; once it's in the white space, it will go wherever your mouse goes. To pick a color, hover the pencil over the desired color. The little gray teardrop will show you what color you're on. Press the down arrow key to press the pencil onto the canvas and start doodling. Press the up arrow key to lift the pencil off the canvas and stop doodling. Press the space bar to clear everything. Adjust the line thickness in the top left corner. Drag stamps to the white space and they will follow your mouse; click on them to stamp.
Want a sprite to become a stamp? Tell me in the comments, I'd be happy to add it!