SMTP is 5321 and defines the transfer protocol. 5322 defines the data format of email -- what you are allowed to pass in as DATA in SMTP -- including the address format in the headers. The concept of a mailbox is introduced in 5321 but the detailed syntax is deferred to 5322.
Nominally, 6531 itself states that the extension does not modify or amend the base specification. It codifies a mechanism whereby compliant implementations can negotiate additional features by mutual agreement. In practice, though, it enables syntax which is outside the scope of the 5322 specification.
A "proposed standard" is a specification which is a candidate to become an official IETF standard, but many RFCs never get past this stage. That does not make them less official or trusted. See http://en.wikipedia.org/wiki/Internet_Standard for an overview of the process.