basati, I had a signal generator as used for industrial measurement in mind, just to be sure that the output isn't spoiled by any side effects a simple circuit might produce.
But probably it doesn't make any difference at all.
On a 10k frequency the first harmonic is 20k, which I could hear easily as a schoolboy - today I have to crank up volume quite a bit to sense a pure 15k tone, beyond 16k there's definetely deafness on my side today...

From a theoretic point of view it shouldn't matter if you listen to an
analog saw, sine or square even from a simple circuit.
Overtones by distortion are at the end of the audible spectrum or beyond.
On a
digital setup this may be different (I actually didn't try it yet), as harmonics may fold back aliasing products into the audible range. As these harmonics are different for different waveforms, the aliasing will provide some information to distinguish the waveforms.
Funny thing is that on a very sophisticated systems you'll have much more problems to distinguish the waves than on a dead cheap one with lots of distortion and aliasing
The ear is an extremely sensitive instrument, that outperforms 98% of all 'technology'.
One of the best microphone preamps the Telefunken V72 has some 120 dB SNR (iirc), the ear's dynamic range is 4 times 'larger' if you assume 132 dB.
The (untrained) ear cannot quantify very well, but then telling numbers isn't the biggest fun in listening to music anyway...
Take a few different preamps with (almost) identical numeric specs and you ears will still be able to tell a difference.
It's difficult to specify (or name) the listening result, but you can clearly distinguish the amps.
To give you a less abstract idea of what I'm talking about check the audio examples in the preamp section of
http://www.basstasters.com
Some (but not all) amplifiers have been recorded with the same bass, pickups and strings so you hear (mostly) the difference between the amps.
cheers, Tom