Navigate to the assignments candidates screen.
The report will come out in the order in which the profiles are displayed on the screen, so set the sort order or grouping first. Next, select the profiles you want to appear on the report (1) - you can also 'Select All', and on grouped sections you can select the whole groups you want to include.
A row of buttons will appear near the top. Click 'Download' (2).
A new window will open that lets you pick what type of report you want (PDF, Word or Excel). PDF have a predefined layout, Word and Excel reports have a layout based on a template. Choose one of these (3), select a report and click 'Generate'.
For Excel reports, there is also an option of using a default excel report instead of a template.