Your question is a little vague. I can't tell if you want to stop processing the array after the first x, or not.
If you're just looking to stop after the first x items, or just looking for the 2nd and 3rd items the solution is to use a slice.
Example: just the first 3:
@user[0,3].each do |user|
... # only executed for user = @user[0],user = @user[1] and user = @user[3]
end
Example: just the second and third:
@user[1,2].each do |user|
... #only only executed for user = @user[1] and user = @user[3]
end
And here's a more specific answer to your question using these new concepts and the content_tag to programatically decide the class of the list item. If you're going to be doing this often, makes a great candidate for a function.
<% first = true %>
<% @user[0,2].each do |user| %>
<% content_tag :li,
:class => first ? "class-for-first-item" : "class-for-2nd-&-3rd" do %>
<%= link_to user.username, user %>
<% end %>
<% first = false %>
<% end %>
<!-- Now to do the rest of them:-->
<% @user[3,-1].each do |user| %>
<% content_tag :li, :class => "class-for-rest" do %>
<%= link_to user.username, user %>
<% end %>
<% end %>