I believe whatever Gmail account you set up, this will be the account used for the phone.
As far as the POP accounts go, I also have 2 accounts set up. All you have to do is select the account you want to send from , press the menu button then press compose.
I also discovered that when you click on a email hyperlink on a web page, a menu will pop up and you can select which email account to send from assuming you have more than one account set up. Hope this helps some in your decision making.

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