I think MarkFive's suggestions are good.
I don't want to speak for my company. But we do exactly what Mark is describing. Users get their Win8 devices either imaged or setup to use their corporate accounts. They additionally link a personal Live account to that account via the Windows 8 linking function. This allows all users access to corporate resources (SkyDrive Pro/SharePoint) via their Windows 8 device - and purchase apps via their personal account. Not only would accounting blow a gasket with it being any other way, but some folks might be embarrassed over their insane amount of purchases they make :)
When the phone is added into the mix, it is set up with the personal (Live.com) account only. But since the corporate credentials and live credentials are linked, it provides access to both sets of resources. While you still access email separately with all of the appropriate EAS security (Corp credentials for Corp email via Exchange, Personal credentials for Live.com, Outlook.com and any others the user wants to add personally), I can browse, view and edit both my personal and corporate docs on my phone or Win8 device with ease. I'm viewing and editing my @live.com-based personal XLS and DOC files shared with friends via SkyDrive right in the same pane in WP8 Office as my corporate (and very secure) SharePoint-based repositories.
I think your problem might be greater because you've created Live.com credentials (meant to be personal accounts) for corporate use. I think that frustrates the value that comes from linking accounts - which fully integrates the best of both worlds between personal and corporate resources.
I hope that helps.