If you've never had intercourse before and the hymen isn't already broken then yes the Pap Smear could break the Hymen.
However most woman who go into the gynecologist for a Pap Smear to be done don't have much of a hymen anyway that could be broken or it may already be broken.
And also if you're menstruating at the time of the Pap Smear then your hymen would not be able to completely cover the vagina and then you would not be able to bleed.
Most times though if you do have a hymen the Pap Smear will not break it although it's still possible.