No Windows RT, atualmente não é possível sincronizar seu conteúdo do SkyDrive. Eu acho que está bem explicado aqui:
Note that because Windows RT is incompatible with externally installed Windows desktop applications, the SkyDrive desktop application is not available for Windows RT devices like the Surface with Windows RT. This means that you can only access your SkyDrive contents through the Metro-style app, which is bundled with RT. And that makes sense: Windows RT is a new mobile operating system, not a hybrid OS like Windows 8, which includes both mobile and desktop components.
Fonte: Windows 8 Dica: Entenda As diferenças entre o aplicativo SkyDrive e o aplicativo SkyDrive