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<?xml version="1.0"?>
<layout>
    <default>
        <reference name="head">
            <!-- ... you have to remove style sheet then add again after the prefered style sheet ... -->
            <action method="removeItem"><type>skin_css</type><name>css/styles.css</name></action>
            <action method="addItem"><type>skin_css</type><name>css/theme.css</name></action>
            <action method="addItem"><type>skin_css</type><name>css/styles.css</name></action>
        </reference>
    </default>
</layout>