The D800E is identical to the D800, save for the different configuration of the sensor's low-pass filter. It's designed to bypass the filter's antialiasing properties and thus produce sharper raw images. Then you have to process the photo in software to remove the artifacts the filter normally takes care of.
Like the D4, the right shoulder features a more dramatic slope than previous models, and the front dial is tilted upward for easier operation--my finger has always gotten a little caught on that red swoosh.
Given that the D700 didn't support video at all, the D800 can't help but be a step up for movie shooters. But it also includes nice capabilities like a headphone jack (in addition to the more common mic jack), uncompressed (albeit 4:2:2) HDMI output and the first USB 3.0 interface on a camera to provide speedier tethered operation. As with the newer Nikon models, the autofocus mode options are accessed by pressing the button on the focus-mode switch.
Except for the addition of a bracketing button on the left side and a record button on the right, the top controls are essentially the same as on the D700. However I suspect that the placement of the record button might make it easy to hit accidentally; plus, I prefer the record button to be on the back where it can be thumb-activated.