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Customers That Get the Confirmation Email
By default, the Customer that placed an Order receives a Confirmation Email. If you have multiple Contacts in one Customer account, the Contact who placed the Order receives the Confirmation Email. In addition, any email addresses added to the Additional Email Addresses field in the Contact or Customer's profile will get the Confirmation Email.
Users and Admins That Get the Confirmation Email
In Setup > Organization > Account, any email addresses listed in the Contact Email or Additional Email Addresses will receive a Confirmation Email after an Order is placed.
If you have Multiple Sites set up, check these boxes in Setup - Organization - Multiple Sites.
Where Can I See Who Got the Email?
Check who received an Email Confirmation in the Messages Tab of an Order.
Click 'Show Content'.
Click Delivery Status at the top to see which email addresses the message was delivered to.
Click 'Details' near the email to view the date and time the email was received by the mail server.
That's how to check who received an Email Confirmation for an Order!
Further Reading