As you know, em
units in font sizes allow the sizes of text elements to retain their proportions relative to other text elements.
There is a method for scalable text in which a "baseline" font size is set on the HTML or BODY element. I generally set this "baseline" font size to 10px because it's a nice round number and makes ems
throughout the site easier to calculate. Say a title is 15px in my design. I would set that title to 1.5em (1.5 x 10px = 15px). You might notice seemingly odd values due to such calculations.
"Fractional" values might also look unusual. For example, "1.33em" is essentially "1 ⅓ em" and "1.67em" is essentially "1 ⅔ em". These accomplish font sizes that are one third and two thirds larger than the baseline, respectively.
If you are designing on-the-fly (without a design comp), you're probably okay just adjusting until it looks right. It's always a good idea to test things by changing your browser's zoom and/or font-size defaults to see how your pages react.