Keep in mind the em is a RELATIVE size - so a 1em is a relative to my container and NOT actual size. A 1, is a 1em based on my browsers default.
So a parent (say .parent) class with a 1em and a child with a 0.75em would be .75 of the parent. A grandchild of that parent with 0.5em would be 0.5em of the 0.75, or approx 0.375 of the original 1em and not 0.5 of that original.
I don't use .px - it is easier to start, but when you need to change everything, you need to change it everywhere - so if you change the 1em to a 1.25em, it also changes the child and grandchild nested within those.
for a concrete example, if I put a margin-top: 0.5em; in a CSS, I am saying to put half the height of my current font as the top margin.
.px - pixels which change depending on the monitor setting and has origins in screen resolution.
.pt - is point, which means that on a printed page, 72 point is approx 1 inch - it has origins in printed material.
% has origins in well, percentage, and I find it more difficult to manage long term.
em has origins in markup.
Most browsers have 12pt (point) font as the base (if I remember correctly), which is 1em, which is - an unknown number of pixels really. SO, off the cuff if I remember .625em is approx 10pt, so if I set the body to .625em, then my .5em below that is 5 point in size, 2em below the body would be 20 point and so forth.
EDIT: my math bites at the end of the day :) so 10/12 is .8333 - so we need .8333 not .625, but you get the idea.