As John said in the previous post, it depends on the skin. As an example, look in your portals\_default\skins directory for the selected skin's .ascx file. In most cases you'll find the main page width setting right at the top such as in DNN-Blue's Horizontal Menu - Fixed Width.ascx:
<TABLE class="pagemaster" border="0" cellspacing="0" cellpadding="0">
<TR>
<TD valign="top">
<TABLE class="skinmaster" width="770" border="0" align="center" cellspacing="0" cellpadding="0">
<TR>
<TD id="ControlPanel" runat="server" class="contentpane" valign="top" align="center"></TD>
</TR>
<TR>
Just change the fixed width to 100%. Remember that if you mod this and re-upload the same skin, your changes will get overwritten so either make the change in the skin locally first and re-add it, or duplicate the skin directory to a new one and modify that one instead. (Copy dnn-blue to mydnn-blue for example). Then select that modified skin from the skins manager.
Hope that helps.