Shadow Shaman is a support hero with amazing lockdown capability and fearsome pushing power, both in terms of wave clearance and building damage output.
Skills
Ether Shock is maxed first but not usually skilled until level 2.
Hex is usually skilled last, but is maxed second after Ether Shock.
Shackles is skilled first for the huge lockdown duration it provides in level 1 engagements but is maxed last.
Mass Serpent Ward is always skilled (levels 6, 11 and 16) and used for hero kills, teamfights, or tower pushes.
Your combo when trying to solo kill an enemy is: Hex > Mass Serpent Ward on top of them > Shackles if you fail to trap them > Ether Shock to finish off.
Items
Starting Items: Courier and/or Observer Wards, Tangos, Healing Salve, Gauntlets of Strength, Iron Branch.
Early Game: Flying Courier, Observer Wards, Boots of Speed, Magic Wand, Bracer.
Core: Arcane Boots.
Extensions: Blink Dagger, Mekanism, Force Staff, Aghanim's Scepter, Necronomicon, Eul's Scepter of Divinity, Refresher Orb, Ghost Scepter, Drums of Endurance, Rod of Atos, Heaven's Halberd, Scythe of Vyse.
Situational: Sentry Ward, Dust of Appearance, Gem (vision), Smoke of Deceit (ganking), Bootso of Travel (late game), Pipe of Insight (if you didn't go Mekanism), Vladmir's Offering (melee cores), Diffusal Blade (anti-Scythe).