1) I can usually tell that you wrote your resume in TeX
2) I then classify you immediately in the "advanced geeks" category, with a "probably hard to work with because is picky" flag...
I personally think it is more about using the right tool for the job than picky-ness. I like the way TeX looks and there are some things that you can do very easily (and maintainably) compared to OO/Word.
I doubt that anyone but very, very few, writes resumes in TeX. LaTeX, yes some. TeX ? Nah.
Someone in command of LaTeX, can make a CV look essentially like whatever they want, so 1) is perhaps not as "usually" as you think.
Regarding 2), what, if anything, do you conclude about an applicant's level of geekiness if you believe you have identified their resume as having been written in Word ?
If you really use this strategy and you are a hiring manager in an area related to technology or computing/programming, someone should seriously consider if it is to their advantage having you involved in the hiring process.
Being picky about your tools and what you produce should be a positive sign. It shows that you care. It doesn't say anything about how flexible the person is.
I wouldn't send out postscript files to people I don't know, since you can't assume that people are able to read them.
I assume your comment was purely about the social point of view? Or are there technical reasons for foregoing postscript documents you may want to print? (Especially reasons that didn't exist 30 years ago.) Thanks!
I wouldn't want to force other people (especially non-geeks) to learn about data formats they don't care about. And after all a pdf is still better than MS Word.