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Most of the rust fighters need time to penetrate. A squirt, then hit it with a wrench doesn't get it. I've done repeat applications over the course of a week with good results. For "upside down valves"; open the valve, squirt enough penetrating oil up inside to get it to start to run back out...

A lot of rusty bolts, plugs, valves want to shear off because you're turning them in the direction the threads are weakest, against lots of years of built-up rust, corrosion, gunk. Try this trick; after a thorough dousing with a good penetrant like Liquid Wrench, Kroil, Marvel Mystery Oil, try...