RFC822 is the historical original standard for the format of email messages.
RFC5322 (which supersedes 2822, which in turn superseded the original 822) defines the basic format of email messages. Its companion document RFC5321 documents the SMTP transport protocol.
These days, you also need to know about mime and the various internationalization features which have been added to the email infrastructure over the years.
The smtp protocol is used for mail transport between servers; for mailbox access from clients, perhaps you need to look at imap and/or pop3.
Resources:
See rfc for more details on the Internet Engineering Task Force RFC (Request For Comments) documents and process.