He reports he can select "32 bit PCM" which my experience can only interpret as 32 bit integer.
If this just some strangeness of the application or could there be some real hardware limitation that prevents capture in floating point format?
All hardware, regardless of what it is, outputs in integer form. That's all it is physically capable of. If something like Audition requests 32-bit floating point format, then it's the driver that provides it, not the sound device. All that happens is that the integer part is converted to a normalized value, and the exponent is filled with zeros. It may
look like 32-bit floating point is being recorded, but actually, it isn't. Well I suppose that in
one form it is, but not one that has any advantage at the recording stage. If you record in 24-bit and convert to 32-bit floating point afterwards, the result is absolutely identical.