1. Open your Outlook 2010 program.
2. Select the Send/Receive tab.
3. Within the Ribbon, Select the small drop down arrow next to Send/Receive and choose Define Send/Receive Groups.
4. When the Groups window appears, make sure the 'All Groups' group name is highlighted and select Edit.
5. In the Edit screen, locate the account you wish to remove from the group. When you have selected the account, Deselect the Check-Box labeled "Include the selected account in this group". This will remove the account from the main Send/receive sessions when you select Send/Receive All.
That's It.
