Do you mean that are not assigned to any project, then it is probably impossible with only this table, the user table is needed as well. If you mean not assigned to a specific projectid then you can do the following:
SELECT user FROM table WHERE user NOT IN (SELECT user FROM table WHERE project = $project)
If you want users that is not assigned to any project you do it in a simular way:
SELECT user.id FROM user WHERE user.id NOT IN (SELECT DISTINCT user FROM table)
Or you can do it with join:
SELECT user.id, projectid FROM user LEFT JOIN table ON user.id = table.user WHERE projectid IS NULL
These queries are untested, so there might be some small syntax problem.