All template files are located in ui/theme/default/ folder.
Please note that, after editing template files directly from here will be replaced when you update. You can do this, if you think you are heavily customizing & you do not want to update.
Admin Layout File-
Admin layout template file is located in-  ui/theme/default/layouts/admin.tpl
Sample codes from Admin layout-
{if has_access($user->roleid,'orders') && ($config['orders'])}
                        {if ($config['orders'] eq '1')}
                            <li class="{if $_application_menu eq 'orders'}active{/if}">
                                <a href="#"><i class="fa fa-server"></i> <span class="nav-label">{$_L['Orders']}</span><span class="fa arrow"></span></a>
                                <ul class="nav nav-second-level">
                                    <li><a href="{$_url}orders/list/">{$_L['List All Orders']}</a></li>
                                    <li><a href="{$_url}orders/add/">{$_L['Add New Order']}</a></li>
                                </ul>
                            </li>
                        {/if}
                    {/if}Client Portal Layout File-
Admin layout template file is located in-  ui/theme/default/layouts/client.tpl
Sample codes from Client Layout-
{if ($config['orders'] eq '1')}
                        <li {if $_application_menu eq 'orders'}class="active"{/if}><a href="#"><i class="fa fa-server"></i> <span class="nav-label">{$_L['Orders']}</span><span class="fa arrow"></span></a>
                            <ul class="nav nav-second-level">
                                <li><a href="{$_url}client/orders/" >{$_L['My Orders']}</a></li>
                                <li><a href="{$_url}client/new-order/" >{$_L['Place New Order']}</a></li>
                            </ul>
                        </li>
                    {/if}By editing those files, you will be able to add / modify / reorder / remove navigation items.