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If Sam & Max is working, does it report SB settings?

Another idea is to enter bios and change the plug and play aware OS to NO or DISABLED. I know having this setting enabled will make some sound cards to choose odd Port, DMA and IRQ settings. There are also some settings in bios to manually redirect IRQs, but i do not advise tinkering with them right now. Just try the plug & play aware os setting first.
Also, enable UPDATE ESCD in bios. Save changes and reboot.

Hmm - would it not be less intrusive to go My Computer -> Properties -> Manage -> Device Manager -> Sound Controllers -> SoundBlaster -> Properties -> Resources and uncheck 'Use automatic settings' -> Click 'Change Settings' and manually set the IRQ's, etc?

Yes, it seems to be a good solution too, but with my method the sound card may even work outside windows. 😎

Is SB16PCI a renamed AudioPCI? Is that chip a ES137x?

If so you could just use the DOS drivers for that chip, possibly.

Sigh. I thought that FINALLY after four full years of XP being mainstream this dead horse would have been beaten for the last time. Apparently not.
There is no DOS in XP. There is a Virtual DOS Machine, NTVDM. The Virtual DOS Machine emulates a Sound Blaster Pro. Having an actual SB16 is completely irrelevant to NTVDM, because it is an EMULATOR. That is why VDMSound exists -- it EMULATES A SOUND CARD. The reason S&M worked was because it found XP's poor SBPro emulation which is default in the XP NTVDM. The actual sound card never ever EVER matters.

Hahha, I didn't see he was running XP.

If you don't know DOS, I don't think you want to try to learn it. Growing up on XP isn't gonna prepare you for DOS whatsoever.... 😀 Getting DOS up and running with PCs designed around it was hard enough. Using modern hardware it will be even harder. You'd want to have a seriously adept DOS buddy to guide you through it if you really want to mess with it.

I'd get DOSBOX and go from there. Don't bother with a SB16 in XP either. Use a newer card, such as a SBLive or newer.

Under Windows XP, sound card type doesn't really matter. What matters is that its drivers will be updated and that the card is working properly...
Mind you, the same ntvdm (NT Virtual Dos Machine), the part of windows NT systems that "emulate" a spartan ms-dos, doesn't even care about the physical "real" sound card installed. It just always emulate a sbpro (I think) and the emulation isn't too good either. You can do yourself a favour by using a VDMSound / DOSBox combination. You will get far better results.

P.S.- As a rule of thumb, (under Windows XP) you should always get the sound card that takes most of the burden off the cpu or the one that suits your needs best.