UrsusArctos: This one little reaction hints at the one thing Asuka truly values: piloting. She equates herself to her skill as a pilot, and she extends that assessment to Shinji.
Line: ...And "No way!" to how this poor railing can support your such huge ego, Asuka :)
SEELE-01: The first real confrontation Asuka had with the idea that being an Eva pilot was something truly special that set her apart, instead of the Freudian nightmare it really was. To Asuka, it is not that Shinji (and later, by extent, Rei) are as good as her: it means she is as "bad" as the other two.
Kendrix: It is important that they let us see his honestly startled response in a ‘private’ conversation – without this, the next scene would probably look a bit different.