Well, to accurately answer that question, I'd have to know a lot about those systems. I've only studied parts of the Gamecube, the rest I have only limited knowledge of their internals. Still, I'd take a guess. I'm only speaking personally from my own experience if I were to take on each.
PS1: Complete guess, but I'd wager that if I can tackle the DS, I'll have a very solid grip on how to approach Sony's first Playstation. The CPU is MIPS, and it should be well documented. I can't speak about the GPU or anything else. 3D stuff isn't my specialty right now, but I'm sure I could do this, given time.
N64: The N64 is a hot mess in terms of documentation, whereas the DS is mostly understood. Whether I'm taking a good LLE path or an advanced HLE path to the N64, I'm going to have to say the DS is easier to get to grips.
Saturn: Again, a hot mess when it comes to documentation. And keeping those CPUs in sync seems like a nightmare. The DS is simpler (has just two, with one running at 1/2 the speed of the main), and saner, and has better games to make testing more fun
PS2: Harder. More "moving parts" or components to emulate. Would take a loooot of time to get anywhere or see any results.
GC: Harder. Same reasons as the PS2.
Dreamcast: Honestly have no idea. I'd assume harder, simply because the DS is something I'm familiar with. Plus, I'd have to buy a bunch of games and hardware to do testing (never owned a DC).
PSP: Moderately more difficult, probably because of the graphical components (again, I'm not too good with 3D things just yet, I'm learning though). An HLE approach to the PSP makes some aspects easy to do, and MIPS is a nice architecture in my opinion.
Yeah, so I imagine just about everything is more challenging than the DS. You have to understand though, I've been working with Nintendo's portables for years. To me, the DS really is an evolution of the GBA (from its CPU to its LCD to various other facets). I know it well, so to go to another system or platform like the advanced ones mentioned above, it would require learning a lot about how they operate. If I had programmed a PS1 emulator, perhaps my outlook on how difficult PS2 or PSP emulation is would be different (I'm sure there are some hardware designs that get transferred or transform each generation).
I first emulated the GB so I could emulate the GBC. I emulated the GBC so I could emulate the GBA. I emulated the GBA so I could emulate the DS. Each step prepared me for the next. I chose this path because I knew it would gradually help me understand how to emulate a DS properly, instead of jumping in all at once. The DS used to scare me; I thought it'd be a long-shot before I could even try to get it running. But now I am confident that I can do it. So now, I do not think the DS is exceedingly hard to program an emulator for (just needs a little time and love). But I know little about other systems, so they seem like HUGE tasks me.