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New users:

• README: Get up-and-running with stack quickly. Requires no prior Haskell tooling experience
• In-depth stack guide: Full tutorial covering all major stack features
• Getting started with stack tutorial

More detailed documents:

• Architecture: for people curious about the internals, wanting to use stack in unusual ways, or wanting to get involved deeply in the codebase
• stack.yaml: Reference documentation for writing stack.yaml files.
• Build command: covers the syntax of the build command and the command line targets

There's also the FAQ which will likely have something for everyone, and the Downloads page (which is linked from the README).