That would require you customizing your site to:
- adjust the templates to ask for a 2nd email address from everyone, and explain why you're doing so
- validate whether any entered email address is legitimate
- adjust the database schema to store the extra info
- write the code to store the info
- adjust the admin template/code to retrieve/show/edit/store that info
- update the core code used to email order confirmations to have it also send again to another email address
Or, instead of changing your store's code you could put the onus on the customer and tell them to create an alias/forwarder in their email account settings so that emails sent to their address are also sent to another address.
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Remember: Any code suggestions you see here are merely suggestions. You assume full responsibility for your use of any such suggestions, including any impact ANY alterations you make to your site may have on your PCI compliance.
Furthermore, any advice you see here about PCI matters is merely an opinion, and should not be relied upon as "official". Official PCI information should be obtained from the PCI Security Council directly or from one of their authorized Assessors.
