I have solved the issue, it was a matter of adding each in the loop I implemented in the view:
<% @player.player_sessions.each do |player_session| %>
<ul>
<li><h4>Highest Score:</h4> <%= player_session.total_score %> </li>
</ul>
<% end %>
After playing around a bit, I realised i didn’t need to add the primary_key option in either of the views, and left the foreign key option only in the Player model.
class Player < ActiveRecord::Base
set_primary_key "alias"
attr_accessible :alias, :avatar
has_many :player_sessions, :foreign_key => "player_alias", :class_name => "PlayerSession"
end
class PlayerSession < ActiveRecord::Base
attr_accessible :player_alias, :total_score
belongs_to :player, :class_name => "Player"
end