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To be able to use the Steam tab in Guild Wars 2, follow these steps:
1: At bottom left in Steam, click +ADD A GAME, non-steam. Check 'Guild Wars 2' and click ok.

2: Right click Guild Wars 2 in steam, and click 'properties'.

3: In the field 'Target', paste this: "C:\Program Files (x86)\Guild Wars 2\Gw2.exe" /Launch=GuildWars2

(if you are a 32-bit user, omit (x86) )

Note that there's the extra /Launch=GuildWars2. This is because you want Steam to run in the GW2 game, not in the login page.

Run from Steam.

Shadows Within[shadowswithin.guildlaunch.com]