It is very rare that a computer monitor will display accurately the color chosen in your layout or in Photoshop. Professionals spend several thousand dollars, time and effort to 'tweak' their systems so that visually the monitor will display as close to possible the printed page. Keep in mind that the two processes are totally different.Red, Green, and Blue are "additive colors". If we combine red, green and blue light you will get white light. This is the principal behind the T.V. set in your living room and the monitor you are staring at now.
Cyan, Magenta and Yellow are "subtractive colors". If we print cyan, magenta and yellow inks on white paper, they absorb the light shining on the page. Since our eyes receive no reflected light from the paper, we perceive black... in a perfect world!
In practice, printing subtractive inks may contain impurities that prevent them from absorbing light perfectly. They do a pretty good job with light colors, but when we add them all together, they produce a murky brown rather than black. In order to get decent dark colors, black ink is added in increasing proportions, as the color gets darker and darker. This is the "K" or "key" component in Cyan Magenta Yellow and blacK printing.
Additive color, or RGB mode, is optimized for display on computer monitors and peripherals, most notably scanning devices. The printing world operates in subtractive color, or CMYK mode.