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I recently did some test overburning with my Plextor, and to my disappointment, I never managed to burn more than 82:30 on a 80-minute CD-R.

I've installed the newest firmware, which should make the drive able to overburn to 99 minutes.

So my questions are:

Is 80-min CD's unsuitable for overburning more than 2:30 (~25 MB)?
Is it just the media I've been using that's at fault? (I've even tried with an Plextor CD-R that came with the drive)

Is the 99 minute burning only audio CDs, or is it possible even with data CDs?

Overburning to 82:30 with an 80 minute disc is pretty good.

If you want to overburn beyond that, pick up some 90 or 99 minute discs.

as Ian said, get some media that is rated for those sizes. Only the Plextor Premium, and some Sanyo drives have the ability to put 99min worth of data/audio onto an 80min CD-R, and they use their own proprietary formats to achieve this (which appear to be very similar to each other).