You don't mention what type of account(s)? (POP, IMAP, Exchange).
You can schedule POP accounts but in Outlook Service Pack 2 (SP2) 14.2.X, IMAP operates as "push mail". You can select to put Outlook into Work Offline mode until you are ready to connect.
It always has an IMAP IDLE command outstanding against the server and will download new email the moment it arrives on the server. For this reason schedules are no longer needed for IMAP accounts. There is no longer a periodic poll for new mail to schedule.
IDLE does not download all new mail the moment it arrives on the serverthis only applies to the Inbox and the folder that you are currently viewing. Instead, SP2 now provides a periodic poll, which is why Schedules are no longer needed