Do not despair. I think you'll find that 32-bit Windows 95 software doesn't use .ini files. It tends to use the Win95 registry, which is actually much more convenient for keeping alternative sets of configuration settings.
What you do is save the branch of the registry containing those configuration settings as a file, with a .reg extension. When you launch a .reg file it puts those settings in the registry, changing your configuration. We discussed this in our August 1996 issue (General Q&A, page 162, Two profiles for Netscape on Win95).
The details for doing the same with Internet Explorer 3 are as follows:
Back up the registry just in case. Make a copy of user.dat and system.dat in the Windows directory. You can also use cfgback.exe, the tool supplied in the Windows 95 CD-ROM in the Other\Misc\Cfgback directory.
Run the registry editor: choose Start menu--Run, type regedit.exe in the Open text box and click OK.
Now locate the branch [HKEY-CURRENT_USER\Software\Microsoft\Internet Explorer]. Highlight the branch by clicking on it.
In the menu, choose Registry--Export Registry File. In the Export Registry dialogue box choose Selected Branch. Now choose a file name like ISP1.reg
Now set up Internet Explorer for ISP2, and save the branch under the name ISP2.reg. If you put a shortcut to these files somewhere convenient, such as the desktop, you can click on them to change configurations before launching Internet Explorer. If you're very brave you can edit the .reg files in Notepad to change settings.
This method works for multiple configurations of any 32-bit application which stores its configuration settings in a branch of the Win95 registry.