The easy way is usually to spot some of the no-no's of layouting; single words at the last line of a paragraph, sentences spanning over page breaks, spacing in block paragraphs, etc.
It's easiest with letters or invoices with some text, where the spacing and word placing is most obvious but you can usually tell in CVs with less text too.
Of course, sometimes Word gets lucky and does a proper layout, but I've found that it's rare that I get to see properly layouted word documents.
However, the Adobe Utopia font, available by using the fourier package, is so much better IMHO.
I'm sure having a LaTeX CV correlates well with other skills which you might deem desirable and, if so, it seems like a perfectly reasonable indicator to use. It shouldn't be used exclusively, but nothing should be.