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Apparently, their Third eyes allow them to see the warp, but they have no psychic powers beyond that.
It says they actually have a third eye on their foreheads. I always assumed it was an analogy for a 'minds eye' or some such. According to Lexicanum
they are fairly useless outside of the Astronomicons light.

I'm guessing Psychic energy lights up the warp for the Navigators. Perhaps the longer it lasts and the stronger it is makes the warp easier it is to navigate. So areas that have brief Psychic flashes would be like introducing you into a new room and flicking the lights on for a second and then off again. Then have people move the furniture as you try to get through the room in the dark.

http://wh40k.lexicanum.com/wiki/Navigator#.T2pJkNVv_6B

By and large, the material forces of chaos travel the galaxy by the same means as everyone else: regular old warp-capable space craft. This is the whole reason why the Cadian Gate is such a big deal to the Eye of Terror. If they could just teleport around willy nilly by the "power of the gods", they'd actually do that, instead of being trapped in a tiny (relatively) sector of space.

Yes, interstellar teleportation happens from time to time, usually by accident. Conventional travel is still the overwhelming majority though.

Chaos plunders worlds by using giant warp worms that drink entire oceans on one end and then crap them out the other end on a different planet. Not joking.

There are many ideals associated with Chaos. Other than seeking immortality, there isn't really an end game... Chaos doesn't want to rule, it doesn't want law and order. (See World Eaters.)

Then again, there are those who worship Chaos that DO want to rule the galaxy with an iron fist (see Black Legion).

It's a personal thing, one worships the Dark Gods to further one's own goals - be it setting the galaxy on fire just to watch it burn, to BLOOD FOR THE BLOOD GOD,! to ruling over humanity.

Medium of Death wrote:It's never really stated how exactly Chaos do it. It probably will be the Astronomicon, but I think they're should definitely be another option. Although that would kind of downplay the importance of the Emperor.

There is still the Astropathic Choir relays. While they enhance the signal, i'm sure by themselves they would generate enough psychic presence for a Navigator to detect.

If not, Daemonic/Possessed Navigators?

The CSM codex claims that possessed marines can be used as navigators. So that's always an option if you have one. They had to be good for something I guess...