I suspect that most people who ask about the possibility of doing multiple PhDs are missing something fundamental in what a PhD is and what it's for. This is an understandable misperception because the general populace knows little about what PhD programs are all about, to the extent that even most people who enroll in a PhD program think they know what they're getting into and then find out that what they had in mind is an approximation to the truth (sometimes a good approximation and sometimes not).
In the various fictive media (novels, comic books, television, film...) having multiple PhDs -- often in confluence with a very youthful persona or explicitly pointed out that they were attained at an early age -- is a standard trope for a certain type of characterization: depending upon the genre it can signal super-genius types, intellectuals, or nerdy/socially awkward types. For instance, Professor Charles Xavier graduated from Harvard at the age of 16, and he holds PhDs in Genetics, Biophysics, Psychology, and Anthropology as well as an MD in Psychiatry. This is obviously meant to be a real-world grounding for his vast mental powers. On the TV show House, the youthful medical student Martha Masters has previously attained PhDs in applied mathematics and art history, and the characterization is less positive: they are not trying to suggest that she's a genius per se -- House is the genius! -- but rather that she has an extremely overachieving personality type.
Of course, Charles Xavier and Martha Masters are fictional characters. Moreover I imagine they were written by people who are not so familiar with PhD programs. In real life, having PhDs in Genetics, Biophysics, Psychology and Anthropology is not the hallmark of a super-genius: rather it would mean that the person is pathologically obsessed with graduate study. PhD's are not merit badges -- more of them is not better. Rather a PhD is the necessary and grueling training for a specific type of professional career.
If you are interested in a subject then you read and learn about it. You get a PhD in a subject because you want that subject to be an essential part of your career (which of course ought to imply that you are very interested in the subject). Moreover, although the PhD provides specific technical training in a certain subject, it does not provide exhaustive training: in most cases people spend the rest of their careers continuing to train in these areas. Rather the point of a PhD is to give you enough specific training so that you can henceforth direct your own training and learning. Otherwise put, a lot of what you do in a PhD is learning how to learn. But learning how to learn is actually a rather robust and subject-independent skill. If you learn how to learn genetics, then if later on your interests turn to psychology or biophysics you will be in a much different and better position to train yourself in these areas. In some ways, doing a PhD in one of these subjects and then turning around and doing another is like becoming an internet millionaire who wakes up one day and decides that she wants to sell electronics...so she shuts down her website, gives all her money away, and starts the business out of her parents' basement. (Or maybe it is like what happens in some of my dreams: I am doing high school all over again, and somehow it is not going as well as it did the first time around.) Why are you starting over from scratch?!?
It is true that "academic transfer" makes better sense between some fields than others. If Martha Masters got a PhD in art history and then decided that she wanted to do applied mathematics instead then she would not have been able to "segue" from one field to the other: she would indeed have had to go back to school. But that makes her story a bit sad, not to mention implausible: getting a PhD is very difficult and very time consuming, but it is not really a feat of strength, and getting two PhDs in two unrelated areas does not show how much of a super genius you are; it shows that you really changed your mind considerably about what you wanted to do with your life and maybe wasted a lot of your time. No matter how smart you are, I don't see how you can get a PhD in art history and then one in applied mathematics without spending at least eight years. You can't just skip to the end and pass the thesis defense by virtue of your preternatural brilliance: there is coursework, residence requirements, and various other mandatory things which necessarily take time. Her character is comic-booky: it is not really plausible that she could have these two degrees and have gone on to be a medical student while still being in her 20's, no matter how brilliant. Moreover, for someone who is that brilliant it would really be sad that she can't seem to figure out anything else to do besides infinite schooling.
Electrical engineering and mathematics are rather closely allied fields. For sure do a PhD in one or the other. While doing a PhD in either one you can choose the amount of involvement you have in the other field, i.e., you can do a very mathematical electrical engineering PhD or a math PhD on a mathematical topic with important applications in electrical networks. Then after you get your PhD you can continue to learn and train in one or both fields as you see fit. It is entirely plausible that you could land an academic job in one department while having gotten your PhD in the other department. This is an ambitious goal, but any academic job is an ambitious goal. Getting the second PhD is unlikely to be directly helpful once you have it, let alone worth the sacrifice of 4-6 years of your life!