Best way(s) to migrate from old iMac to new iMac?

My 2007 iMac, bless its engineered heart, is dying. (I am amazed that could run OS 10.9.3) My new iMac (27", 3.5GHz, 3TB Fusion drive) is arriving any day now.

What is the best method to port everything (apps, Preferences, data, Libraries, etc.) to the new iMac? The old iMac is routinely backed up hourly with Time Machine to an external drive, for which I am acquiring a Thunderbolt to Firewire adapter.