Set the z-index of the :before or :after pseudo element to -1 and give it a position that honors the z-index property (absolute, relative, or fixed). This works because the pseudo element's z-index is relative to its parent element, rather than <html>, which is the default for other elements. Which makes sense because they are child elements of <html>.
The problem I was having (that lead me to this question and the accepted answer above) was that I was trying to use a :after pseudo element to get fancy with a background to an element with z-index of 15, and even when set with a z-index of 14, it was still being rendered on top of its parent. This is because, in that stacking context, it's parent has a z-index of 0.
Hopefully that helps clarify a little what's going on.