doc kmeans
shows the
function signature. If you look at the options for 'Name', 'Value' pairs you will see that 'Start' allows you to input your own starting positions.
As for what is a valid choice, simplest way is to try them and find out. In some cases they may not converge to where you want, in others they may do. Without random initialisation it is a 100% deterministic algorithm though so it would only be a single test to get the 1 answer in each case (although there are, of course, an infinite number of ways to place evenly distributed points around that circle)..