The Bithead will always be superior, but the difference will grow exponetially at higher bitrates. The fact of the matter is. Heres the chain you data goes through:
Data --(through DAC)--> Line-out Signal --(through Amp)--> volume adjustable signal --(through headphones)--> sound waves also known as music.
Now, in this buisness every signal piece of the chain is upgraded from standard iPod buisness. Better headphones make for better sound waves. Better amps make for better sounding signals. The fact of the matter is that. iPods's amp, dac, and stock headphones are crap cause they have to be so small and cheap. So, for the iPod setup, you have replaced the Amp and headphones making for a much more enjoyable system. Yet, for the laptop you are replacing the DAC, Amp, and headphones making for complete control of the whole chain. Plus the Bithead's DAC and Amp are matched to be perfect matches for each other.
So, there are only two instance when your iPod will sound better or come close. Itll come close when the files are like less than maybe 256, because with less data to work with obviously a DAC would become less and less useful if that makes any sense. A DAC improves the clarity and soundstage by better translating every bit into a signal. Yet, if there are fewer bits and less information about the song, then the DAC can't do as much. Clarity could be lost in encoding not DAC.
And the other is preference. I use the Bithead, but find its Amp so laid back, though detailed, that it bugs me. I find the highs too sharp with my Etys, the mids lack a punch, and the bass is either there or not. I don't like the Bithead's sound signature. So, while I love the compact DAC/Amp Combo, I can't stand the sound, which makes me have a hard time listening to it. I'm hoping a Tomahawk will be better paid out of the line-out of my iPod than the Bithead for my tastes, since its a different sound signature and made for Etys. Yet, I'm sure the detail and soundstage wouldn't be as accurate or authentic as the Bithead. Yet for me, enjoying the music isn't all about those things, so I'm selling mine.
Yet, if you like its sound. Yes, Laptop is better than iPod all the time, even though the difference may not be worth it if songs are encoded bad.
Ohh I didnt realize you would be using another amp after the Bithead..... thats a tough one. The longer the chain the worst to manage. I would imagine itll still sound better. But you would have to play around with volumes a lot.