You can read the information on Meta Stack Overflow under "How do I change my OpenID":
This is documented on the Stack Overflow blog.
Go to your user page and click add openid or change openid.
http://blog.stackoverflow.com/wp-content/uploads/openid-multiple-association-2-new.pngNote that once both are populated, the primary OpenId will be overwritten if you associate another OpenID.
You can use the [swap] link (not pictured) to switch your primary and secondary OpenID at will.
After changing, beware that copying your profile to other accounts does not copy the OpenID details.