With the Razer Naga, I've already added several spells into the PvE rotation, though I haven't done any of the requisite mathes. Solar Beam-ing a spell casting mob, causing them to charge you, followed by a Typhoon, is a fun way to aggravate mobs and keep damage down. But I Googled around a bit to see if anyone has The Right Way to rotate these spells I've now got at my thumb-tip.
Elitist Jerks seemed to have the best guide:
This is a compendium of information on raiding as a Balance Druid. It contains everything a beginner needs to achieve basic competence at raid DPS, as well more detailed discussion for people more interested in understanding the theory or more advanced play. The article is supplemented by the attached spreadsheet.
I haven't mathed up Starsurge, but I think it's to your advantage to cast even in the midst of an eclipse, something Jerks seems to agree with, though it's written just ambiguously enough I won't swear to it.
Casting Starfall during Lunar isn't something I'd considered closely enough. Good point.
EDIT: For some reason, I conflated Thorns and Roots, below. Honestly, I've completely forgotten about Thorns. In the Recruit-a-friend, I'm playing with a druid who is Thorning, and I caught the mistake. I should throw it onto the Naga rotation.
Honestly, though, this is the sort of stuff that kills the enjoyment for part-timers like me, yet I'm just math-inclined enough (and efficiency worried) that I keep getting drawn back in. There's probably also a small tinge of worry that a PUG might get upset that I'm not using my skillz The Right Way. I don't know why. I've never been called out for not putting out enough dps.
And, honestly, for PvE, the fights are too short for maxing DPS and Innverate too good at keeping you at max mana for much to matter, afaict. Fire and forget.
In any event, Jerks' is a good guide, and the Naga really does change the way I play.