This is a fairly old post, but I stumbled upon it looking for something on Google. I just wanted to add a few comments relevant to the topic though.
I just picked this app up recently and I have mixed feelings about it.
One great thing about the app is that it's universal, so I can install it on both my iPad and iPhone, only paying the $0.99 fee once. Moreover, there's no additional fees to download headphone profiles. If you have several pairs of headphones, you can download the profiles for all of them. This let's you switch quickly between headphones on the device or install new headphones when you buy new ones.
I'll try to describe the sound, but I'm a total newb when it comes to these audiophile forums and I have never written a review. So I apologize right now if I use some incorrect terms or language that is not the usual jargon.
I absolutely love the software for my Etymotics MC5 in-ear phones. They make the sound much more lush. It fills everything out for you. I get that these headphones are supposed to be flat and as close to neutral as possible. I thought I wanted that in a headphone and I was seriously mistaken. The sound is flat and boring. It's dull and uninspired. I like a neutral sound, but there is absolutely no character to these headphones at all. The Audyssey profile brings these headphones alive. Filling out the sound exactly where it needs to be without over-emphasizing any particular range over another.
But here's the rub, I don't particularly care for Audyssey for my Grado SR80i headphones. I really love the character of Grado's headphones and I find that Audyssey actually takes away from that character. It takes the punchiness out of the bass and gives the sound and overall more muddy, rolling tone that I don't particularly care for. So a lot of times I just turn it off when I'm using my Grados. I also own a pair of Grado iGi earbuds (which frankly I like a hell of a lot more than the MC5s), but Audyssey doesn't actually have a sound profile for them, so I don't even know if it would improve the sound there.
So for me Audyssey Media Player is a mixed bag. At the end of the day, I would suggest spending the small fee to try it out yourself. If you like it use it. I know there's a lot of audio snobs out there that turn their nose up at such things, but at the end of the day what's most important is the enjoyment that you get out of your setup.