It's going to be fairly easy to test this. You take one group of people who haven't smoked in the last few hours and you test them. Make sure it doesn't go off. You take another group who have smoked (I'm sure plenty of college students would be happy to sign up for this trial) and you test them, make sure it does go off. It's pretty simple. It's a machine with an empirical number, so you don't even have to do this double blind.
And if it doesn't give good results? It won't hold up in court. Every lawyer defending someone with a positive result (whether false positive or true positive) will argue that the device isn't accurate and the case gets tossed (or even the ability to use these as evidence). If it doesn't hold up in court, police really won't have much incentive to use these anyway.