This is something I definitely wasn't aware of, but I'm the type of person that doesn't usually require phone support - and if I get to the stage where it doesn't work on my smartphone, quick, it gets uninstalled and I go into a fit of internal rage.
But, the Google Play Store actually features 24-hour technical support over the phone. So if you have any problems with purchasing or downloading apps, movies or music, you can fill out an online form and a Google representative will call you during your requested time.
The Play Store 24-hour technical support is only for Play Store-related problems, not handset-related problems. So I'm sure they would be picky on what they would help you out on, which is fair enough. If you want to have a handy link to contact the people at Google Play, try this link. Not bad, huh?