this is a topic I have some first hand experience with.
One of my audio hobbies is two track ambient recordings of live music. For several years now, i've been mastering at 24bit and various sample rates from 44.1 > 96kHz.
all things on the playback side being equal...24bit audio sounds MUCH better than redbook. Of that, my ears are certain.
Of course, I always made redbook copies of these recordings to enjoy on my main system, and in the car...etc. I used quality software (wavlab) and the apogee uv22hr dithering scheme (which sounds awesome) to bring the bit depth to 16 from 24, and resample if necessary.
I used to take these newly mastered redbook copies and put them up agaist the 24bit raw LPCM files played through my recording gear and digitaly into my stereo, which at the time consisted of a Musical Fidelity CD-PRE24...a great sounding CD player and DAC/PRE combo. I could utilize the onboard transport for the redbook copy, and just run through one of the digital inputs for the 24bit files. The DAC in this unit would upsample any digital input...including ones from the transport...to 2496 upon playback. Worthy of mention...24/96 streams would also be resampled and not locked to an external clock...even when it didn't need to be.
End result...
It was *very* difficult, if impossible, to tell a difference between the raw 24/96 file and the redbook file that was being upsampled to 24/96 by the DAC.
Since then, i've changed my stereo around dramitcaly.
I can still do the same tests, and I find that the upsampled redbook info sounds 95% as good as playing high-res PCM to begin with. So, I took a different approach. I now focus my attention on the upsample at the playback end. I still master in 24bit, but I dont see much of a need for in terms of playback. Not at least for what i'm doing. Studio work is a different animal all together, so that doesnt' apply here.
Bottom line, get a good upsampling DAC....or CD deck w/an upsampling DAC, and you will definatly have a better sounding rig.