How to pick two colors side by side to make a painting overall balanced while make the main subject stand out? It's a process of intensive decision-making among the effective colors. To achieve the most simultaneous contrast, complementary colors give you it. However it's a wild beast and can easily go out of your control. The more you know color theory and wisely use the color palette will help achieve the more successful results. It works to both traditional and digital art medium. I found the article from COLOR VISION & ART very informative and got lots of examples comparing art in the past(before 1900) and nowadays.
Check it out here-
http://www.webexhibits.org/colorart/contrast.html
Another precise and easy to understand explanation by Richard McKinley :
Simultaneous contrast teaches us that everything is affected by its opposite. Something will look lighter when placed next to something dark, and warmer when placed next to something cool, and visa versa...
The middle value strip looks darker or lighter depending on its relationship to the other values.


