Yes, that’s the right idea. A couple notes:
In the parlance of census summary data, B25063 is a single table, and B25063_003 through B25063_026 are variables within that table. Through IPUMS NHGIS you would select the B25063 table once (for each source ACS dataset) and that would get you all of the variables in the table… no need for requesting each variable 003 through 026 separately. In the Census API, I think tables are referred to as groups, but you could still request just a single group.
As suggested in my reply to your question about the limited selection of ACS year ranges in time series tables, it’s problematic to use 5-year ACS data to construct annual estimates. It sounds like you’re still planning to include all 5-year ranges in your analysis, which would include many largely overlapping samples. For most applications, I would recommend instead analyzing only non-overlapping 5-year periods if possible.
A related point: the 5-year estimates do not represent characteristics for any single year. E.g., the 2016-2020 5-year estimates represent characteristics throughout that 5-year period, not just 2020.