public class UserExtension
{
    private final User theUser;

    public UserExtension(ApexPages.StandardController stdController)
    {
        this.theUser = (User)stdController.getRecord();
    }

    public Map<String, Map<String, Boolean>> getMap()
    {
        Map<String, Map<String, Boolean>> theMap = new Map<String, Map<String, Boolean>>();
        theMap.put('Outer 1', new Map<String, Boolean> { 'Inner 1' => true, 'Inner 2' => false });
        theMap.put('Outer 2', new Map<String, Boolean> { 'Inner 1' => true, 'Inner 2' => true });
        return theMap;
    }
}

<apex:page standardController="User" extensions="UserExtension">
    <apex:pageBlock >
        <apex:repeat value="{!Map}" var="outerKey">
            {!outerKey}
            <apex:repeat value="{!Map[outerKey]}" var="innerKey">
                {!innerKey}
                {!Map[outerKey][innerKey]}
            </apex:repeat>
        </apex:repeat>
    </apex:pageBlock>
</apex:page>

<apex:page standardController="User" extensions="UserExtension">
    <apex:pageBlock >
        <apex:pageBlockTable value="{!Map}" var="outerKey">
            <apex:column value="{!outerKey}"/>
            <apex:repeat value="{!Map[outerKey]}" var="innerKey">
                <apex:column headerValue="{!innerKey}">
                    {!Map[outerKey][innerKey]}
                </apex:column>
            </apex:repeat>
        </apex:pageBlockTable>
    </apex:pageBlock>
</apex:page>