There are lots of regulations and safety issues for handling refrigerant. I am afraid it seems you aren't aware based on this question. I am fine helping you understand what is wrong, but please don't consider this as encouragement to vent refrigerant or some other bad move.
This site has great info for beginners:
Troubleshooting with Gauges FAQ
The pressure should be equal when the engine/compressor is off. Something weird there.
The high side pressure should be much higher when running (car on and AC set to max).