Adobe Colour CC (formerly Kuler) is a great site for exploring the relationships of colours. Using an interactive wheel you can compare a variety of relationship types (i.e. complementary) and build standard 5 hue palettes based upon this.
It is an internet application designed specifically for exploring colour space all allowing users to download palettes directly into Adobe applications such as Photoshop, Illustrator and InDesign. The fully manipulable palette also provides RGB codes that can be taken into other design applications.
The great thing I found about using this is I can locate a precise hue I want to use and this can calculate complementing hues in relation to whatever style of palette I decide to construct. This tool supports the idea of the ‘Hollywood Look’ as if you locate skin tones with a complementary palette it will choose to contrast and mix the palette with teal and blue hues.