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Originally Posted by Tarquinius

ROTF Movie line is basically self contained within the movie and features "movie figures"

Yes, to a point. It is self-contained in that it has movie toys and off-screen "movie" characters, but nothing that strayed too far outside that universe and design aesthetic. The last wave or so began to show the direction that HTFD would go, with more blended aesthetics that blurred the line between movie and non-movie styling.

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Generations is a continuation of a previous line called Classics which then evolved into Universe 2.0 (So it goes classics-universe 2.0-generations)

Exactly correct. Generations is also a little broader than its predecessors since it not only has "classic"-style designs, it also has other niche stuff like toys based on the War For Cybertron video games.

And technically, Power Core Combiners is its own separate subline and not part of Generations. It's in the same red packaging, but does not bear the "Generations" tag under the TF logo. It has a PCC logo instead.

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Hunt for Deceptacons goes either way, it just being its own line which has movie esque figures but may have one or two random ones thrown in there which would supplement the Classic/Generation theme.

Also correct. HFTD is to Revenge of the Fallen as Pursuit of Cobra was to Rise of Cobra. Basically it's a transitional line that contains the movie stuff with a few toys that could easily display with Classics or Movie toys. Eventually it will become RTS, which will lead into The Dark of the Moon toy line (aka TF3).

As for what to look for, nostalgia plays a big factor for most TF collectors. But on toy merits alone, here are a few to check out for each line. Keep in mind, all of these suggestions are based on toys I actually own:

Generations: Get pretty much everything in this line. Probably one of the best lines Hasbro has done in years and it continues the excellent work done for Classics and Universe 2.0. To give you an idea, Generations Thrust is a remold/redeco of Classics Starscream (one of many remold/repaints out there) and Generations Red Alert is a remold/redeco of Universe 2.0 Sideswipe (which is also used to make Sunstreaker, but with a clever twist on reusing the mold. Sunstreaker came first, btw). Also, the WFC toys are great, especially Soundwave and Prime (haven't found Megs yet).

Power Core Combiners: Some of these are hit-or-miss for me. Nothing horrible, but some aren't that special. So far my favorites are Bombshock (although watch the Jeep leg; connector point is a little loose), Leadfoot, Icepick and Smolder. Definitely get Leadfoot, if only for Pinpointer. Pinpointer is arguably the best Minicon ever made.

Revenge Of The Fallen: The entire scout class. Every one ranges from good to awesome. There are some redecos (a couple molds have 3 different paint schemes), but at the very least try to pick up one of each mold.

As for the larger classes, I'd recommend Autobot Skids and Mudflap, Brawn, Jetfire, Optimus Prime (Leader and Voyager), Recon Ironhide, Bludgeon, Lockdown, and Mindwipe. Leader-class Prime and Jetfire have a combined mode that is just massive and rivals Brave Series combiners for sheer bulk, plus it still has decent articulation!

Hunt For The Decepticons: The entire scout class again. Continued from ROTF, but new molds mixed in with the redecos. Other good picks include Legends Devastator (TRU Exclusive), Legends Ravage, Sea Spray, Ironhide, and Hailstorm.

Like nakobass said, there's even more goodness on the horizon for all three (four) lines. And definitely look into the older Classics/Universe 2.0 lines. There were some real gems in those two lines as well.