. In order to change your username, you need to do so on Twitter itself. You can find the link to do so here:
http://support.twitter.com/articles/14609-how-to-change-your-username
Once you change your username on Twitter, you can remove and re-add your account in TweetCaster (go to the gear icon from the menu, select accounts then tap "Edit” in the upper right and then tap the "-" next to the account name) and it will reflect the new username.