ok, im presuming that you are creating the list using xml and not querying in .cs?
whats the full code and are you doing it like this?
<Query>
<OrderBy>
<FieldRef Name="SomeUserField"/>
</OrderBy>
</Query>
You dont need to add in ascending = true as by default it is ascending. You only need to use it if you want to go in decending order by setting it to false!
and that should be encapsulated in the view like so:
<View BaseViewID="0" Type="HTML" MobileView="TRUE" TabularView="FALSE">
<Toolbar Type="Standard" />
<XslLink Default="TRUE">main.xsl</XslLink>
<ViewFields>
<FieldRef Name="Title"/>
<FieldRef Name="SomeUserField"/>
</ViewFields>
<Query>
<OrderBy>
<FieldRef Name="SomeUserField"/>
</OrderBy>
</Query>
</View>
http://msdn.microsoft.com/en-us/library/microsoft.sharepoint.spsitedataquery.viewfields.aspx
for orderby query reference to this for help :)
orderby
http://msdn.microsoft.com/en-us/library/ms467378.aspx
full xml list (Query Schema)
http://msdn.microsoft.com/en-us/library/ms467521.aspx
hope this helps :)
EDIT
ok that would make sense :) , have you tried the following? tbh without seeing your code I wouldnt know where your going wrong!
SPQuery spQuery = new SPQuery();
spQuery.Query = "<OrderBy><FieldRef Name='SomeUserField' /></OrderBy>";
SPList list = web.GetList(listUrl);
SPListItemCollection items = list.GetItems(spQuery);
You can find more indepth here:
http://msdn.microsoft.com/en-us/library/ms457534.aspx
EDIT
If you want to replace the SPFieldUser to SPUser.name for the real name you need to cast or convert the object and loop through each one.
SPFieldUser userField = (SPFieldUser)item.Fields.GetField("LoginName");
SPFieldUserValue userValue = (SPFieldUserValue)userField.GetFieldValue(item["LoginName"].ToString());
SPUser user = userValue.User;
As an example the above code gets the spuser from the SPFieldUser. "LoginName" is the colum name your refering to change. Sorting on any list is possible, in the end its text your sorting on and its in a list!
for more of an understanding you should checkout this:
http://aarohblah.blogspot.co.uk/2009/11/converting-list-item-to-spuser-object.html
and
http://edinkapic.blogspot.co.uk/2007/08/getting-spuser-out-of-spfielduser.html
I hope its what your looking for or again iv missunderstood you lol.
hope it helps :)