Re: Windows 7 Pro 32bit and Workgroups
I wish I had some magical advice that would help you in the decision making process but unfortunately I do not. I don't have the resources to replicate your intended environment but I can tell you that I have had no issues using Windows 7 Ultimate 64bit, in a mixed Windows environment (5 computers, Vista Business, XP Pro, Win 7 32bit and 64bit Ultimate and Pro) simple workgroup (No HomeGroups). Aside from some very minor printer driver issues (32bit vs. 64bit) which were easily corrected and one legacy HP Scanner issue, all client nodes get along well with each other happily sharing files/folders and printers without problem.
My one suggestion would be, to the extent possible, introduce the new build Windows 7 machine (consider 64bit to take advantage of memory in excess of 3gigs) onto the network in a reasoned and stepped process, attach a printer and share it, create a folder share and assign the appropriate share and ntfs permissions and determine if any of the other network nodes have any issues connecting to those resources before moving over all your critical data and finding yourself in a hair on fire situation with more problems than solutions available. With that approach you'll have an opportunity to address and resolve issues before they reach critical mass.
WARNING: There are always legacy software as well as legacy hardware issues to consider. With a new build the hardware shouldn't be as much of an issue use the Windows Hardware Compatibility Site if you have concerns and look for Windows7 Logo Branded Products where applicable. Software is another issue, like hardware something that runs great and works well on Windows XP may not always perform as expected on a Windows 7 machine. There are some work arounds using various compatability settings but generally you need to consider checking with the software vendor for any known issues with Windows 7 and any updates/upgrades that you may have to purchase which may impact the bottom line (price) of moving to Windows 7.
Worse case, you'll end up with a machine that will really run XP well.
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)