Take a look at the Amazon S3 API documentation to get a feel for what can and can't be done with Amazon S3. Note that there are two APIs, a simpler REST API and a more-involved SOAP API.
You can write your own code to make HTTP requests to interact with the REST API, or use a SOAP library to consume the SOAP API.
Fortunately for Android developers, Amazon has released a (Beta) SDK that does all of this work for you. There's a Getting Started guide and Javadocs too. With this SDK you should be able to integrate S3 with your application in a matter of hours.
The Getting Started guide comes with a full sample and shows how to supply the required credentials.
Conceptually, Amazon S3 stores data in Buckets where a bucket contains Objects. Generally, you'll use one bucket per application, and add as many objects as you like. S3 doesn't support or have any concept of folders, but you can put slashes (/) in your object names.