From RFC 5321, section 2.3.11:
The standard mailbox naming convention is defined to be “local-part@domain”; contemporary usage permits a much broader set of applications than simple “user names”. Consequently, and due to a long history of problems when intermediate hosts have attempted to optimize transport by modifying them, the local-part MUST be interpreted and assigned semantics only by the host specified in the domain part of the address.
So yes, the part before the “@” could be case-sensitive, since it is entirely under the control of the host system. In practice though, no widely used mail systems distinguish different addresses based on case.
The part after the @ sign however is the domain and according to RFC 1035, section 3.1,
“Name servers and resolvers must compare [domains] in a case-insensitive manner”
In short, you are safe to treat email addresses as case-insensitive.