I'm afraid I don't agree with Boo on this. To be 'on one's toes' is to act in an alert and eager manner, often to impress the person concerned rather than worried about him/her.
"The Managing Director of the company is visiting us today, so I expect all of you to be on your toes" is a typical sentence you might hear the phrase used in. In other words, "Be alert and show lots of enthusiasm so that the BIg Boss goes away with a good impression of us here."