Serial communication in LV is done through an abstraction layer called VISA using the VISA VIs. Open the Example Finder (Help>>Find Examples) and search for "serial" to see some examples.
To learn more about LabVIEW, I suggest you try searching this site and google for LabVIEW tutorials.
Here,
here,
here and
here are a few you can start with and
here are some tutorial videos. You can also contact your local NI office and join one of their courses.
In addition, I suggest you read
the LabVIEW style guide and the LabVIEW user manual (Help>>Search the LabVIEW Bookshelf).
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