I am playing a Shaman for Solo and a Healer for my Dup with a friend. For my Shaman should I go 100% Cave for 100% solo PvE or should I go a % into Cave and Aug?

I played mostly solo to 39. You can go without Aug but I highly recommend getting 12 Aug for endu2. Makes kiting much easier. I never died to mobs until now, only ministrels and nightshades (and Fyi ^^).
At some time around 30 I also put 7 in mending for poison/desease dispell.
So max subterr with some Aug.
Try to get RR 1L4 for MCL and Long wind.

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I have both on almost the same level... maby i go on 37 Cave (second Insta-Desease) - 38 Augh (all yellow incl. Endu 4) and rest in Mending (9 or something) at the end.

It´s a good spec to level and farm. Also - if everyone has LW1 - a good Spec for RVR with Permasprint. Or Solo-RVR/Smallgroup.

For Cave you can go 41 Cave (Last Bolt and DD), 34 Augh (Endu 3) and 8 Mend (The Spec from Runental)

Or maybe the BB-Style... 46 Augh, 27 Cave and Rest in Mend...

But for me... 37/38/9 is the way...