(Not to be confused with Xunit, a popular .Net unit testing library.)
Today in a fit of boredom I started inspecting Gmails DOM (yes, I was very bored).
Ever
Note that, terms like "single/double line spacing" actually mean the offset between two adjacent lines, measured by em. So "double line spacing" means each line has a height of 2 em.
Therefore, if you want to specify a vertical distance that is proportional to "lines", use em. Only use ex if you want the actual height of lowercase letter, which is, I dare say, a much rarer instance.
UPDATE: The web standard allows the browser to use either 0.5em as ex or derive from the font.
However, there is no way to reliably embed any "x-height" information in a font (OpenType or webfont).
Hence, the former possibility makes the ex-unit redundant, and the latter lacks any reliable means to happen. And the fact that either is possible makes it even less reliable.
Thus I argue for the lack of value of the ex-unit.