Adding a second library:
Right-click on the library icon -> Switch/create library -> Use a previously existing library at the chosen new location.
Navigate to the location of your second library and click OK.
Merging two libraries:
This can only be done after you've added the second library. Select all the books in the library you want to merge, right-click and select Copy to library. After the books have been copied to the second library, you can delete the first library (right-click on the library icon -> remove library; note that you can only delete a library you're not currently in). For finding any duplicate books after merging, you can use the Find Duplicates plugin.
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