I have been working with Adobe Illustrator for quite a while and I've never encountered this problem. When I pick a color the Color Picker shows the right values, but the color displayed in the artboard is different.
I'm working on RGB mode and have all my settings in sRGB mode. I have tried changing the View Mode to CPU, I have recalibrated my display, but nothing seems to work. This just affects how colours are displayed and not the actual file and colours in it.