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So I'm starting up a Dark Angels force, with a focus on deathwing. Problem is, I have no idea of what color paints I might use. Also, I'm a bit rusty on highlighting a blending so if you guys could help me out that'd be fantastic!

I'm not sure how much work you want to devote to each model, but here's a "quick and dirty" way to knock out a lot of DW pretty quick (I'll use the GW paint colors that were standard when I painted DW, but any equivilant should work):

Base model with Krylon Fusion: Satin Dover White
Wash with 1/2 Devlan Mud mixed with 1/2 water
Highlight with 1/2 Bleached Bone mixed with 1/2 Skull White
Optional final highlight with Skull White

Paint Green bits Dark Angel Green
Highlight with 1/2 Dark Angel Green mixed with 1/2 Goblin Green
Optional final highlight with Goblin Green

Paint weapons and other bits however you paint weapons and other bits.

Sorry I don't have a finished example, I painted these for someone almost 5 years ago.

Depends: theres a lot of options (which is surprising, considering their armor colours). Typical is white with layering to tone down the colour. Other ideas is the old bleached bone colour (not sure what the new one is called).
I opted to go for something even easier. Tamiya colour (the little spray cans you see at pretty much every RC car/model plane store) has a colour called "wooden deck tan". Spray the deathwing models with this, then do a heavy black/brown wash, and instant "dirty deathwing". After that, all thats left is green and red. Amazing contrast on snow bases too!

Mine is actually very basic and I will list it out here, I have a kitbash Belial in my gallery that should show my general scheme as well.

Prime: P3 White
Basecoat: Ushabti Bone
Wash: Seraphim Sepia
Light Greys: Astronomican Grey (Wash with Nuln Oil)
Greens: Caliban Green (Highlight with Snot Green)
Purity Seals: Vallejo GC Dead White.
Skin: Elf Flesh (old GW)
Golds: Shining Gold (Old GW)
Gun bits: Leadbelcher
Red Bits: Evil Sunz Scarlet.

If you have any questions on mine that I didnt list out here, please feel free to shoot me a message and hope this helps, I absolutely love Deathwing and I find them to be a joy to paint.

Try this: http://fromthewarp.blogspot.com/2011/09/how-i-paint-deathwing-bone-armour.html

While you are there, check out some of his other articles about blending and highlighting... they are definitely worth a read.

Here's what I did to get my dudes looking like this:
Armor:
- Prime with Army Painter's Skeleton Bone spray, then touch up any areas missed with their Skeleton Bone bottled paint
- Wash whole model Agrax Earthshade
- Paint model again with Skeleton Bone, but leaving the recesses untouched
- Highlight with GW Screaming Skull, with Ceramite White (or any pure white really) for the extreme edges

Green:
- Paint with Caliban Green/Army Painter's Angel Green. Over the Bone basecoat, the thinner green paint actually gathers in the recesses, effectively washing the area for you. If it doesn't, a green wash will do the trick.
- Highlight with Warboss Green, with a Skarsnik Green extreme edge

Red:
- Khorne red, with an Agrax Earthshade Wash
- Bring back up to Khorne red, leaving the recesses untouched
- Highlight with Mephiston Red, with Squig Orange (IIRC) for extreme edges
- Use these same colors for eye lenses, with a dot of white in the far edges

Metal:
- Leadbelcher washed with Nuln Oil
- Drybrush/highlight with Runefang Steel

Gold:
- Balthasar Gold
- Gehenna's Gold, leaving Balthasar Gold near the recesses
- Auric Armor Gold highlight

Hey thanks guys! this has been very helpful