OK, I've read this four times now, and I'm not sure why the XPmachine\Username and password doesn't work and without knowing what domain environment these machines are actually in and what possible array of associated group policy objects / OU memberships may be impacting their ability to avail themselves of external (not domain) network resources by way of alternate (not domain) credentials I really don't have an answer. But I might suggest a not so elegant and possibly not so desireable work around. Would it be possible for these users on these particular travelling laptops to have a local login to resolve to a local user account on the local Windows7 laptop with the necessary permissions to locally stored files and folders. I believe that would take the laptops domain membership out of the equation and allow these users to still get their respective work done when out of the office. Like I said, probably far from a preferred solution but a possible option. I know that I have a Windows 7 pro machine joined to my SBS 2003 domain and I can still logon to my wife's XP pro(non domain member) machine from the Win7 machine using the XPmachine\username without issue. However, I cannot say that this resolves because her workgroup name is the same as the actual domain name or rather because I have no GPOs or complex OUs outside of the default domain policies.
Yesterday was, Today is, but ahh Tomorrow...mystery, suspense and a promise of hope.

Operating System Windows 7 Ultimate 64 bit
Computer Type Home built
OS Service Pack Service Pack 1
Internet Explorer Version IE9
DirectX Version 11
CPU Type and Speed AMD Phenom II X6 1090T Black Edition Thuban 3.2GHz
CPU Cooling Stock Factory Cooler
CPU Idle Temp 32C
Motherboard Chipset GIGABYTE GA-870A-UD3 AM3 AMD 870
System BIOS Revision Award F5a (beta) 11/15/2010
System Memory Type G.SKILL Ripjaws Series 16GB (4 x 4GB) 240-Pin DDR3 SDRAM DDR3 1333 (PC3 10666)
System Memory Speed 1333 currently underclocked to 1066
System Memory Clocking 7, 7, 7, 20
Video Card Type and Speed Nvidia GeForce GTS 450 1Gig DDR5 DX11
Video Card Cooling stock
Video Card Temperature 32C idle
Power Supply Unit (PSU) Antec EarthWatts EA750 PSU
Computer Monitor Dual Dell ST2320L
Sound Card Integrated RealTek HDA
Speakers Klipsch
Headset/Microphone Altec Lansing
Hard Drive Two Seagate 500 gig SATAII's ST3500418AS ATA
Optical Drives Lite-On DVDRW x2
Keyboard and Mouse Logitech USB Optical
Modem-Router Type Arris MODEL: TM602G / Microsoft MN700
Network Adapter Realtek RTL8102E/RTL8103E Family PCI-E Fast Ethernet NIC
Printer HP InkJet 990cxi
Network Speed WD Passport 500gig USB 3.0 BackupDrive
USB Controller NEC Electronics USB 3.0 Root Hub
Gaming Console Xbox 360
Anti-virus Software Microsoft Security Essentials
Productivity Suite Office Pro Plus 2010
System Install Date 2011-01-25 21:59:23 on this drive
Computer Skill Level Certified Professional
Windows Experience Index 7.2
Favorite Game FarCry (original, 2 sucked)