The HR department's "inflexible procedures" are there to save the company money. Which do you think is higher: the activation energy (in terms of time, money, resources, and frustration) to retrain and retool the HR staff to accept resumes i whatever format (PDF, LaTeX, ODF, etc.) or the activation energy it takes you to stop whining and use Word like everybody else?
It doesn't make you a staffer from ManPower. The CEO probably submitted a Word resume.
The CEO probably doesn't even have a resume in the sense that you're thinking of. He is playing a different game entirely, where all decisionmaking authority rests with a handful of identifiable people who he is selling directly. You want to be playing his game.
This is a subjective matter. I'm not whining. I'm asserting quite clearly: you will never get a resume from me in a format other than PDF.
You, as an individual, are free to apply to those jobs with a Word resume. I won't bother. I will be absent from their candidate pool. In my book, that is very much not a problem.
It doesn't make you a staffer from ManPower. The CEO probably submitted a Word resume.