How can I get emails for my 1st degree connections?

Email collection is available for Expert mode users only, the Regular user interface does not provide this option.

In order to capture the email addresses of your 1st-degree contacts, please go to "My Network" and click to see all contacts. 

Or you can simply set up a LinkedIn search and filter your connections by 1st degree.

 Then wait for the list to load and when you see a green popup saying "At your service", click on "Visit profiles" 

Now Dux-Soup will go through the list and record the information about a profile which you can later download.