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When underprinting WHITE (i.e. you want white underneath your color) you must have the top layers, colored shapes, or images set to "Overprint Fill"

 

This is available in the Attributes panel of Illustrator.

 

If this is not set the color will print without white, creating a metallic effect. This can be seen in the middle demo.

 

A correct example of underprinting white can be seen in the example graphic on the right. The barrels, stars, text shadow, and tagline will print metallic, as there is no white underneath them.

 

Turning on "Overprint Preview" allows you to see this example as well.