Have you tried a small test area of roof wash strength and see if it comes off? A 70/30 to start. If no results, A 60/40 ratio... You shouldn't need any high pressure. Make sure you pre-wet everything below the stain and keep it wet while testing the stain. It's best to have a second (fresh water) hose on the ladder with you and keep a small amount of running water flowing across the face of the area just below the stain! Otherwise, You may end up having to treat the entire chimney!!!
Keep us posted with your results...
Mike