Today at work over lunch I was on wi-fi and started to download a big playlist via iTunes Match (iPhone 5 iOS 6). It was happily downloading multiple songs in parallel. A little while later I went for a walk outside, got a couple of "error connecting to network" popups, thought that was normal. Got back inside to my desk back on wi-fi and checked on the download, but now it was only doing one song at a time. So I thought I'd pause it by turning wi-fi off, put the phone down and went to do some work for a bit. A while later I went back and noticed my phone was warm. I then noticed that it was still downloading songs! I went into settings and verified that "Use Cellular Data" was turned off for Music, iTunes and iTunes Match, and yet in front of my eyes it was happy gobbling up my data plan over LTE. A usage check showed 4.6GB out of my 4GB... :-(
I called Apple and they had never heard of this, had me reset network settings, etc, no change (still downloading), so I ended up just turning off iTunes Match. I then called AT&T and they will remove the charges (once they show up, only the first 3.something GB is in thei system yet).
I am going right over to Apple bugreports now to open a bug. It seems that only initiating a download using iTunes Math (at least) checks the settings; a transition to a different network (e.g. cellular-only) is apparently not triggering a re-check that should pause the data transfers. Meh!