Right-choose a word and select Add to dictionary.
And changing the default spell check controls is easy too.
In the menu, click Tools, then Options, and go for the Spelling tab in this dialog.
But theres no obvious way to edit your custom dictionary.
Live Writer actually stores your custom dictionary entries in a plain text file located in your appdata folder.
It is saved as User.dic in the C:\Users\user_name\AppData\Roaming\Windows Live Writer\Dictionaries folder.
Microsoft Office Word also stores its custom dictionary in a plain text file.
Then copy the words, and past them into your Live Writer custom dictionary file.
%AppData%\Microsoft\UProof\Custom.dic
Dont forget to save the changes when youre done.