Well my purchase has already been made, and I will likely never hear the Pico, although I do place a lot of value on the positive comments it's garnered here in its young life.
Still, I would be reluctant to believe it could outperform the Duet as a DAC. Speaking from a purely functional standpoint, I would not choose something like the Pico over the Duet for my own needs. I don't need to take an amp and DAC along with me everywhere I go in my pocket. I've had a Hornet for about a year and have taken it along with me to the office about twice since I've owned it, so I personally see very little value in ultraportability since anything extra to attach to the likes of an iPod simply isn't worth it away from the nightstand where its rightful home is.
The design of the Duet is far more ergonomic, and desktop friendly. It has a normal 1/4" headphone jack, which is already a significant improvement over the Pico's more limiting mini jack. I would much prefer to use mini-to-1/4" adapters for headphones when necessary rather than the other way around. Also, the Pico really doesn't have "standard" line outs for feeding an external headphone amp if you should want to use one. The Duet's breakout cable, while ugly, can easily be dangled down over the back of a desk or table, and normal high-quality interconnects can be used to feed various audio gear. There is also no rechargeable battery to worry about, and FireWire (in my opinion) is a better interface than USB. The size of the Duet is a plus, as it won't go sliding around the desk like a Pico would. Finally, if you found you were pleased (which I think you would be) with the headphone section of the Duet, you could just use it and then have many other I/O options at your disposal via the breakout cable, such as feeding powered monitors.