Several factors to consider here:
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The obvious location and geographic differences. Take your pick.
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Curriculum differences: Penn has a core curriculum in that 7 area distribution requirements must be met by choosing exclusively from a limited list of courses i each area. One of these is foreign language which means demonstrating foreign language proficiency and which therefore can require anywhere from 1-4 courses unless you can place out of it without any courses. In contrast, Williams has distribution requirements but course selection is wide open to meet those requirements.
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Special Academic Experiences: Williams has winter semester which sounded like a super fun learning opportunity to me when I did a formal visit there. Courses are specially designed for that 3-week term. Williams also has tutorials available which are rare at any college on this side of the Atlantic. I’m not aware of special learning opportunities at Penn, so that’s something for you to look at for this comparison.
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Research university vs LAC: student:faculty ratios at the two colleges is similar, so I expect that faculty access is pretty similar. But when it comes to access to research, I expect that the priority at Penn goes to grad students first. To the extent that professors involve students in their research, the priority for student involvement at Williams will always go to undergrads.
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The English departments at both schools are great. When I look at Psych courses offered at the 2 schools, the two departments feel very different to me. The Penn courses are mostly academic and traditional, probably great preparation for someone who wants to go on to a graduate program that does a Loy of research. The Williams course list is littered with topical courses, meaning ones more related to issues in society which would be of more general interest. They also have the courses that would prep their students for grad school. I’m not favoring one approach over the other, but I think that you as the student will probably find one or the other more appealing. Take a look and see for yourself.
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English & Psych are 2 of the most popular majors at Williams, but not so much at Penn. However the College of A&S at Penn is 3 times the enrollment of that at Williams, so the number of English majors is about the same at the 2 schools while Psych, which is more popular at Penn than English is, has almost double the number of majors as at Williams. Shows the difference in size. English & Psych are more popular at Williams but in raw numbers, there are as many or more in this major at Penn.
Bottom line is that Penn is big (10,000 undergrads, 25,000 total) and it is urban. William is small (2100 total enrollment) and very rural.neither is better than the other, but they are definitely different even though both are top notch. No one can make this call for you.