Here's a little test data set I made, with three dummy People.
I opened Notepad, copied this in, (if you want to try this, you will need to add an extra return after the last line of data) and saved it as a .csv.
"First Name","Last Name","Mobile Phone","E-mail Address"
Then, I used the "Import from File" on Outlook.com and got something looking like this.
I can then click on the email address and it sends an email in Outlook.com (well, except for aa_Test2 who doesn't have an email address).
In the Windows 8 Start Screen apps, I went into the People App, waited a few seconds until it synchronised, and again I could then send an email within Windows 8.
I've called them all names beginning with "aa_" so they should be easy to find and delete!
Does any of this work for you?